Oxide perovskite and porous glass composite material and preparation method thereof

Abstract

The invention discloses an oxide perovskite and porous glass composite material and a preparation method thereof, and belongs to the technical field of composite materials. The oxide perovskite and porous glass composite material provided by the invention comprises oxide perovskite and a metal organic framework (MOF) material, wherein the MOF wraps the oxide perovskite. The oxide perovskite and porous glass composite material disclosed by the embodiment of the invention has high stability and high fluorescence property, the tolerance of perovskite to water and oxygen is greatly enhanced while the excellent photoelectric property of the perovskite is ensured, and the perovskite with high stability and excellent photoelectric property is obtained. According to the preparation method of the oxide perovskite and porous glass composite material provided by the embodiment of the invention, the oxide perovskite and porous glass composite material can be produced at low cost and in a large scale.

Description

Technical Field

[0001] The present invention relates to the technical field of composite materials, and in particular to an oxide perovskite and porous glass composite material and a preparation method thereof. Background Art

[0002] Perovskite materials possess many exceptional properties, which have led to their widespread application in many fields. For example, they offer excellent optoelectronic properties. Perovskites possess exceptionally strong light absorption, over 10 times that of crystalline silicon. This means that under the same lighting conditions, perovskites can absorb a wider spectrum of light, including ultraviolet and visible light, thereby improving photoelectric conversion efficiency.

[0003] However, the metal halide perovskites used in existing technologies have poor water and oxygen stability. Therefore, new perovskite materials are needed to meet practical needs. Summary of the Invention

[0004] The present invention aims to address at least one of the technical problems existing in the prior art. To this end, the present invention provides an oxide perovskite and porous glass composite material and a preparation method thereof. The oxide perovskite and porous glass composite material has high stability and high fluorescence properties. The preparation method enables the low-cost and large-scale production of the oxide perovskite and porous glass composite material.

[0005] The oxide perovskite and porous glass composite material according to the present invention comprises an oxide perovskite and a metal-organic framework material (MOF), wherein the MOF encapsulates the oxide perovskite.

[0006] The oxide perovskite and porous glass composite material according to the embodiment of the present invention has high stability and high fluorescence performance. While ensuring the excellent photoelectric performance of the perovskite, it greatly enhances the tolerance of the perovskite to water and oxygen, that is, a perovskite with high stability and excellent photoelectric performance is obtained.

[0007] According to some embodiments of the present invention, the MOF is a zeolitic imidazolate framework (ZIF).

[0008] According to some embodiments of the present invention, the MOF is selected from one or more of ZIF-4, ZIF-8, ZIF-62, ZIF-76, etc.

[0009] According to some embodiments of the present invention, the oxide perovskite is doped with rare earth elements.

[0010] According to some embodiments of the present invention, the rare earth element includes one or more of europium, terbium, yttrium, erbium, etc.

[0011] The method for preparing the oxide perovskite and porous glass composite material according to the present invention comprises the following steps:

[0012] S10: taking an appropriate proportion of perovskite precursor materials, dissolving them in a polar solvent, filtering the solution, and heating them at a certain temperature for a certain time to synthesize oxide perovskite crystals;

[0013] S20: Dissolve zinc nitrate hexahydrate, imidazole (Im), and benzimidazole (BIm) in a polar solvent in an appropriate ratio, heat at a certain temperature for a certain time, and then cool to room temperature at a certain rate to obtain a MOF;

[0014] S30: heating the MOF obtained in step S20 in a tube furnace from room temperature to a certain temperature, and then cooling to room temperature;

[0015] S40: mixing the oxide perovskite crystals obtained in steps S10 and S30 and the MOF in a certain ratio and grinding them together so that the MOF wraps the oxide perovskite crystals to obtain an oxide perovskite and porous glass composite material;

[0016] S50: placing the oxide perovskite and porous glass composite material obtained by the S40 step into a tubular furnace for heat treatment, and performing heat treatment at a certain heating rate under the protection of flowing inert gas; when the sample reaches the specified temperature, immediately taking the entire tubular furnace out of the furnace, and quenching it directly by immersing it in liquid nitrogen under the protection of inert gas.

[0017] According to some embodiments of the present invention, the step S10 further includes the following steps: washing the oxide perovskite solution after heating with methanol several times, and then drying it in a vacuum oven for a certain period of time, thereby synthesizing the oxide perovskite crystal;

[0018] And / or the S20 further includes the following steps: washing the obtained MOF with methanol several times, then drying and heating it in an oven at a certain temperature for a certain time, and taking out the MOF for standby use.

[0019] According to some embodiments of the present invention, the polar solvent in step S10 and / or step S20 is N,N-dimethylformamide (DMF).

[0020] According to some embodiments of the present invention, the MOF in step S30 is ZIF-62.

[0021] According to some embodiments of the present invention, in step S40, the oxide perovskite crystals and MOF are ground by ball milling.

[0022] Additional aspects and advantages of the present invention will be set forth in part in the description which follows and, in part, will be obvious from the description which follows, or may be learned by practice of the present invention. BRIEF DESCRIPTION OF THE DRAWINGS

[0023] The above additional aspects and advantages of the present invention will become apparent and readily understood from the following description of the embodiments with reference to the accompanying drawings, in which:

[0024] Figure 1 is a photograph of an oxide perovskite (ABO3) and porous glass composite material and a pure perovskite material under bright field rain 365nm ultraviolet light according to an embodiment of the present invention;

[0025] Figure 2 (CsPbO3) according to an embodiment of the present invention 0.25 (agZIF-62) 0.75 Changes in relative PL intensity over time when immersed in water;

[0026] Figure 3 (CsPbO3) prepared according to the embodiment of the present invention 0.25 (agZIF-62) 0.75 and powder X-ray diffraction pattern after storage at room temperature for 650 days;

[0027] Figure 4 (CsPbO3) according to an embodiment of the present invention 0.25 (agZIF-62) 0.75 PL stability under continuous laser excitation;

[0028] Figure 5 (CsPbO3) according to an embodiment of the present invention 0.25 (agZIF-62) 0.75 Thermal stability test of composite materials;

[0029] Figure 6 It is prepared by the hydrothermal synthesis of the precursor according to the embodiment of the present invention (CsPbO3) 0.25 (agZIF-62) 0.75 representation of;

[0030] Figure 7 (CsPbO3) prepared at different sintering temperatures according to the embodiment of the present invention 0.25 (agZIF-62) 0.75 PL spectra and ultraviolet-visible (UV-Vis) absorption spectra of the composite materials (A) and the corresponding normalized spectra (B), and ultraviolet-visible (UV-Vis) absorption spectra (C);

[0031] Figure 8It is prepared by adopting different sintering temperatures and then low temperature quenching under Ar protection according to the embodiment of the present invention (CsPbO3) 0.25 (agZIF-62) 0.75 Full width at half maximum (FWHM) and exciton lifetime of the composites;

[0032] Figure 9 1 is an XRD diffraction pattern of ZIF-62 obtained by adjusting the ratio of blm to Im according to an embodiment of the present invention. DETAILED DESCRIPTION

[0033] The following describes embodiments of the present invention in detail. Examples of the embodiments are shown in the accompanying drawings, wherein the same or similar reference numerals throughout represent the same or similar elements or elements having the same or similar functions. The embodiments described below with reference to the accompanying drawings are exemplary and are intended only to explain the present invention and are not to be construed as limiting the present invention.

[0034] In the description of the present invention, it should be understood that descriptions involving orientations, such as up, down, front, back, left, right, etc., indicating orientations or positional relationships, are based on the orientations or positional relationships shown in the accompanying drawings. They are only for the convenience of describing the invention and simplifying the description, and do not indicate or imply that the device or element referred to must have a specific orientation, be constructed and operated in a specific orientation. Therefore, they cannot be understood as limitations on the present invention.

[0035] In the description of the present invention, "several" means one or more, "many" means more than two, "greater than," "less than," and "exceed" are understood to exclude the number itself, while "above," "below," and "within" are understood to include the number itself. The use of "first" and "second" in the description is solely for the purpose of distinguishing technical features and should not be construed as indicating or implying relative importance, implicitly specifying the number of the indicated technical features, or implicitly specifying the order of the indicated technical features.

[0036] In the description of the present invention, unless otherwise clearly defined, terms such as setting, installing, and connecting should be understood in a broad sense, and technicians in the relevant technical field can reasonably determine the specific meanings of the above terms in the present invention based on the specific content of the technical solution.

[0037] Reference below Figures 1 to 9 The oxide perovskite and porous glass composite material and the preparation method thereof according to an embodiment of the present invention are described.

[0038] The oxide perovskite and porous glass composite material according to an embodiment of the present invention includes oxide perovskite and a metal-organic framework material (MOF), wherein the MOF encapsulates the oxide perovskite.

[0039] The oxide perovskite and porous glass composite material according to the embodiment of the present invention has high stability and high fluorescence performance. While ensuring the excellent photoelectric performance of the perovskite, it greatly enhances the tolerance of the perovskite to water and oxygen, that is, a perovskite with high stability and excellent photoelectric performance is obtained.

[0040] The term "perovskite" is used herein according to its ordinary meaning in the art to refer to the "perovskite crystal structure" of certain oxides, rather than specifically to perovskite material (CaTiO3).

[0041] The general structural formula of oxide perovskite is also ABX 3， Here, X is an O element.

[0042] MOFs are crystalline porous materials with periodic network structures formed by the self-assembly of metal ions or metal clusters with organic ligands. These materials exhibit significant potential for applications in gas storage, gas separation, catalysis, drug delivery, sensing, and proton conduction, due to their high porosity, large surface area, tunable pore size, and surface functionalization.

[0043] In some embodiments of the present invention, the MOF is a zeolitic imidazolate framework (ZIF).

[0044] ZIF, or zeolitic imidazolate framework, is a porous crystalline material. In ZIF, organic imidazolates are cross-linked to transition metals to form a tetrahedral framework. ZIF materials offer high stability, high porosity, and organic functionality, making them particularly suitable for efficient catalysis and separation processes.

[0045] Both ZIF and MOF have three-dimensional pore structures, with metal ions or metal clusters as connection points and organic ligands as support to form a spatial 3D extension. However, the framework structure of ZIF is more special, showing a tetrahedral shape.

[0046] The metal ions in ZIFs are usually transition metals, while the organic ligands are imidazolate compounds. This composition gives ZIFs a certain uniqueness in structure and properties.

[0047] Due to its high stability, high porosity and organic functionality, ZIF has wide applications in efficient catalysis and separation processes.

[0048] In summary, ZIF, as a subset of MOF, has certain particularities in structure and composition, and exhibits unique advantages in efficient catalysis and separation processes.

[0049] In some specific embodiments of the present invention, MOF is selected from one or more of ZIF-4, ZIF-8, ZIF-62, ZIF-76, etc.

[0050] The chemical formula of ZIF-62 is [Zn(Im) X (BIm) 2-X ] (where X≥1.75), different specific structures can be obtained by adjusting the ratio of imidazole to benzimidazole. It is worth mentioning that when one H on the benzene ring of benzimidazole is replaced by Cl, the same process can be used to obtain the porous glass material of the ZIF-UC-5 series, whose chemical formula is [Zn(Im) X (BIm) 2-X ](X≥1.75).

[0051] On the other hand, Zn in ZIF-62 can also be replaced by other atoms in different proportions.

[0052] In some specific embodiments of the present invention, the oxide perovskite is doped with rare earth elements.

[0053] Due to their unique electronic structure and energy level distribution, rare earth elements (such as europium, terbium, yttrium, erbium, etc.) can be doped into oxide perovskites to form effective luminescence centers, thereby giving the material luminescence properties.

[0054] In some specific embodiments of the present invention, the rare earth elements include one or more of europium, terbium, yttrium, erbium, etc.

[0055] Specifically, europium-doped calcium titanate (CaTiO3:Eu) can emit red light, while terbium-doped calcium titanate can emit green light.

[0056] The method for preparing the oxide perovskite and porous glass composite material according to the present invention comprises the following steps:

[0057] S10: taking an appropriate proportion of perovskite precursor materials, dissolving them in a polar solvent, filtering the solution, and heating them at a certain temperature for a certain time to synthesize oxide perovskite crystals;

[0058] S20: Dissolve zinc nitrate hexahydrate, imidazole (Im), and benzimidazole (BIm) in a polar solvent in an appropriate ratio, heat at a certain temperature for a certain time, and then cool to room temperature at a certain rate to obtain a MOF;

[0059] S30: heating the MOF obtained in step S20 in a tube furnace from room temperature to a certain temperature, and then cooling it to room temperature;

[0060] S40: mixing the oxide perovskite crystals obtained in steps S10 and S30 and the MOF in a certain ratio and grinding them together so that the MOF wraps the oxide perovskite crystals to obtain an oxide perovskite and porous glass composite material;

[0061] S50: The oxide perovskite and porous glass composite material obtained in step S40 is placed in a tube furnace for heat treatment, and the heat treatment is performed at a certain heating rate under the protection of flowing inert gas; when the sample reaches the specified temperature, the entire tube furnace is immediately taken out of the furnace and quenched directly by immersing in liquid nitrogen under the protection of inert gas.

[0062] The preparation method according to the embodiment of the present invention can mass-produce oxide perovskite and porous glass composite materials. Addressing the shortcomings of traditional synthesis methods, which often result in low yields, the method proposed in the present invention can achieve rapid mass production of perovskite materials.

[0063] Furthermore, in step S10, the filtered solution is heated at 120° C.-140° C. for 4-6 hours, after which yellow needle-shaped crystals are observed.

[0064] Furthermore, the filtered solution was heated at 130° C. for 5 hours, and then yellow needle-like crystals were observed.

[0065] Furthermore, in step S20, the MOF is heated in an oven at 120°C-140°C for 3 to 5 days, and then cooled to room temperature at a rate of 0.5°C / min-1.5°C / min to obtain the MOF.

[0066] Furthermore, in step S20, the MOF is heated in an oven at 130°C for 4 days and then cooled to room temperature at a rate of 1°C / min to obtain the MOF.

[0067] Furthermore, in step S30, the MOF crystal sample is heated in a tube furnace at a temperature range of 200-500°C from room temperature, and then cooled to room temperature. The heating rate is controlled at 5-30°C / min, and the cooling rate is controlled at 20-500°C / min.

[0068] Furthermore, in step S40, the grinding method includes a series of mechanochemical synthesis methods such as a crusher, a sand mill, and a grinder.

[0069] Furthermore, in step S50, heat treatment is performed at a heating rate of 20°C / min under the protection of flowing Ar2. When the sample reaches the specified temperature, the entire tube furnace is immediately taken out of the furnace and quenched directly by immersing in liquid nitrogen under the protection of Ar2.

[0070] In some specific embodiments of the present invention, S10 further includes the following steps: washing the oxide perovskite solution after heating with methanol several times, and then drying it in a vacuum oven for a certain period of time to synthesize oxide perovskite crystals;

[0071] And / or S20 further includes the following steps: washing the obtained MOF with methanol several times, then drying and heating it in an oven at a certain temperature for a certain time, and taking out the MOF for standby use.

[0072] Methanol is used to clean the perovskite solution and MOF, which does not react with the perovskite itself, does not dissolve the perovskite, and is easy to remove.

[0073] Furthermore, in step S10, the perovskite solution after heating is washed three times with methanol, and then dried in a vacuum oven for a certain period of time to synthesize oxide perovskite crystals.

[0074] Furthermore, in step S10, the perovskite solution after heating is dried and heated in a vacuum oven for 24 hours to obtain oxide perovskite crystals.

[0075] Furthermore, in step S20, the obtained MOF is washed three times with methanol, and then dried and heated in an oven at a certain temperature for a certain time, and the MOF is taken out for use.

[0076] Furthermore, in step S20, the MOF is then dried and heated in an oven at a certain temperature for a certain period of time, and then taken out for use.

[0077] Furthermore, in step S20, the MOF is dried and heated in an oven at a temperature of 70° C. to 90° C. for 12 to 36 hours, and then taken out for later use.

[0078] Furthermore, in step S20, the MOF is dried and heated in an oven at 80° C. for 24 hours, and then taken out for later use.

[0079] In some specific embodiments of the present invention, the polar solvent in step S10 and / or step S20 is N,N-dimethylformamide (DMF).

[0080] In some specific embodiments of the present invention, ZIF-62 is selected as MOF in step S30.

[0081] The chemical formula of ZIF-62 is [Zn(Im) X (BIm) 2-X ] (wherein, X≥1.75), different specific structures can be obtained by adjusting the ratio of imidazole to benzimidazole.

[0082] In some specific embodiments of the present invention, in step S40, the oxide perovskite crystals and MOF are ground by ball milling.

[0083] By ball milling, different ratios of perovskite and ZIF-62 (ratio ranging from 1:1-1:20) were mixed and ground to obtain the final oxide perovskite and porous glass composite material: (PVK)X (ZIF-62) 1-X (Where X is the mass percentage of each component, PVK is perovskite).

[0084] For ball milling, first select a planetary ball mill with an appropriately sized jar (e.g., 20ml, 150ml, or 200ml), an orbital speed of 60-800rpm, and an autorotation speed of 30-400rpm. A ball-to-material ratio of 1-20 is recommended, and the grinding balls should be made of suitable materials, such as stainless steel or zirconia. The diameter of the grinding balls ranges from 1-10mm, with a large-to-small-ball mass ratio of 1:10. (A variety of grinding ball diameters are available: the large balls primarily crush the material, while the small balls primarily mix it; this can be adjusted based on the intended purpose.)

[0085] The size of the grinding balls can be determined based on the weight and hardness of the material. When producing in small batches and the material is relatively fragile, a combination of grinding balls with diameters of 1mm, 3mm, and 5mm can be used, with a corresponding mass ratio of 6:3:1. If the material is relatively hard, the proportion of large balls can be increased appropriately, for example, a mass ratio of 5:3:2 is more suitable for crushing experiments. For large-scale production, five different diameter grinding balls can be used simultaneously, with a mass ratio of large and small grinding balls of 5:2:1:4:7. The specific ratio can be adjusted appropriately according to the experimental production scenario. The ball milling time range is controlled between 10-120 minutes, and the ball milling speed range is controlled between 400-1000rpm.

[0086] The preparation method according to the embodiment of the present invention has at least the following beneficial effects:

[0087] The oxide perovskite and porous glass composite materials prepared by the hydrothermal method are combined together through an adjustable ball milling method to form liquid glass-wrapped PVK at high temperature. After annealing, an oxide perovskite and porous glass composite material with high stability and high fluorescence performance (high quantum yield, high chromatographic purity, and high yield) is obtained.

[0088] By adjusting the ball milling parameters, the fluorescence properties of oxide perovskites can be controlled. Different ball milling parameters can produce perovskites of different particle sizes. Generally speaking, longer ball milling time and more grinding balls are more conducive to obtaining smaller particles. Compared with non-uniform, larger particles, uniform and fine perovskite particles generally have higher internal quantum efficiency.

[0089] The stability and fluorescence effect of PVK are maintained through heat treatment process.

[0090] PVK is wrapped by porous liquid glass at different temperatures and forms a stable PVK composite system through different annealing conditions.

[0091] During the mixing process of PVK and porous liquid, the phase transition temperature of both will decrease to form PVK materials with excellent external quantum yield and fluorescence properties.

[0092] Large-scale production is possible. Aiming at the disadvantage of low yield in traditional synthesis methods, the method proposed in the present invention can achieve large-scale production of oxide perovskite materials in a short time.

[0093] It can achieve uniform grain size of oxide perovskite, which is more suitable for application in display devices.

[0094] Specific embodiments and various aspects of the present invention will now be described with reference to the following non-limiting examples.

[0095] Example 1 - Photographs of oxide perovskite (ABO3) and porous glass composite materials and pure perovskite material under bright field rain 365nm ultraviolet light.

[0096] For example Figure 1 As shown, the preparation method of the oxide perovskite and porous glass composite material proposed by the present invention is used to prepare (CsPbO3) 0.25 (agZIF-62) 0.75 and pure perovskite CsPbX3, where X is chlorine, bromine, or iodine. Both were sintered at 275°C.

[0097] The two materials were placed under bright field rain with 365nm wavelength ultraviolet light and photographed. The results are as follows: Figure 1 As shown in Figure 2, under bright field conditions, both groups of materials exhibit different colors, indicating that different phases of perovskite materials are formed. Under ultraviolet irradiation, the fluorescence effect of the oxide perovskite and porous glass composite material far exceeds that of the pure perovskite material. The pure perovskite material exhibits almost no fluorescence, while the composite material exhibits a significant fluorescence effect.

[0098] Example 2-(CsPbO3) 0.25 (agZIF-62) 0.75 Changes in relative PL intensity over time when immersed in water.

[0099] For example Figure 2 As shown in FIG, the oxide perovskite and porous glass composite material was obtained by the preparation process of the present invention, and aging tests were performed on it. Under the experimental conditions of immersion in water for 10,000 hours, storage in the environment for 650 days, mild heating and continuous laser excitation, the oxide perovskite and porous glass composite material showed strong stability. The specific experimental data are shown in FIG. Figure 2 shown.

[0100] Example 3-(CsPbO3) 0.25 (agZIF-62) 0.75 And the powder X-ray diffraction pattern after storage at room temperature for 650 days.

[0101] For example Figure 3 As shown, the samples were sintered at 350 °C and then quenched at low temperature.

[0102] Example 4-(CsPbO3) 0.25 (agZIF-62) 0.75 PL stability under continuous laser excitation.

[0103] For example Figure 4 As shown, the excitation laser energy density is about 57mW / cm 2 The samples were sintered at 300 °C and then quenched at low temperature.

[0104] Example 5-(CsPbO3) 0.25 (agZIF-62) 0.75 Thermal stability test of composite materials.

[0105] For example Figure 5 All samples were prepared by sintering at 300°C. (A) Graph shows the change in PL intensity during 1000 cycles of heat treatment (30-100°C) in flowing Ar (20 mL / min). (B) Graph shows the change in PL intensity during 1000 cycles of heat treatment (30-80°C) in flowing air (20 mL / min).

[0106] Example 6 - Preparation of (CsPbO3) using a hydrothermal precursor 0.25 (agZIF-62) 0.75 representation.

[0107] For example Figure 6 As shown, (A) is the powder XRD pattern of single crystal δ-CsPbO3 synthesized by hydrothermal method. (B) is the powder XRD pattern of ZIF-62[Zn(Im) 1.95 (bIm) 0.05] Powder XRD patterns of (CsPbO3)(agZIF-62) (25 / 75). Data were collected under a constant flow of nitrogen (20 mL / min). The samples were dried under vacuum before thermal testing. The temperature ramp rate was 20°C / min for the first upscan and 10°C / min during DSC cooling and the second upscan. (D) Powder XRD patterns of composites prepared at different sintering temperatures. Composites prepared with mechanochemical precursors are inserted as reference. (EF)(CsPbO3) 0.25 (agZIF-62) 0.75 Secondary electron (SE) and backscattered (BSE) SEM images of (CsPbO3). Scale bar is 1 μm. The sample was sintered at 300 °C and then quenched at low temperature. (G) (CsPbO3) prepared with different precursors 0.25 (agZIF-62) 0.75 Comparison of absolute PLQY of composites. Both samples were prepared by ball milling for 1 h and then sintered at 275 °C.

[0108] Example 7 - (CsPbO3) prepared at different sintering temperatures 0.25 (agZIF-62) 0.75 PL spectrum and ultraviolet-visible (UV-Vis) absorption spectrum of the composite material (A) and the corresponding normalized spectrum (B), and ultraviolet-visible (UV-Vis) absorption spectrum (C).

[0109] For example Figure 7 As shown, perovskite and ZIF-62 were prepared by hydrothermal method, and then the two were mixed together by ball milling to prepare (CsPbO3) 0.25 (agZIF-62) 0.75 In the ball milling process, different sintering temperatures (175℃-350℃) were used, followed by low-temperature quenching. The obtained oxide perovskite-ZIF-62 composite materials were characterized, and the results are shown in the figure. (CsPbO3) 0.25 (agZIF-62) 0.75 The composite material begins to show red PL emission after sintering and quenching at 175℃, and the strongest PL is obtained at 275℃ ( Figure 7 A). Higher sintering temperature causes the PL maximum to red shift ( Figure 7 B), while a decrease in the optical band gap was observed ( Figure 7 C).

[0110] Example 8 - (CsPbO3) prepared by sintering at different temperatures and then quenching under Ar protection 0.25 (agZIF-62) 0.75Full width at half maximum (FWHM) and exciton lifetime of the composites.

[0111] For example Figure 8 As shown in Figure 2, the temperature change also leads to a reduction in defect density and enhanced uniformity of the CsPbO3 composition, as evidenced by a reduction in the full width at half maximum (FWHM) and an increase in the excited-state lifetime. Compared to slower quenching, the rapid low-temperature quenching resulted in materials with the best PL lifetimes and PL quantum yields (PLQYs) (>50%).

[0112] Example 9 - XRD diffraction pattern of ZIF-62 obtained by adjusting the ratio of blm to Im.

[0113] For example Figure 9 As shown, using different ratios of imidazole and benzimidazole in the hydrothermal process for preparing porous glass can produce porous glass with varying surface morphologies, allowing for control of pore size, specific surface area, melting point, and glass transition temperature. In actual production trials, porous glass with different morphologies can provide various adsorption conditions for perovskite crystals, facilitating the selection of the most suitable porous glass.

[0114] For ZIF-62, the xbIm content was increased / Im content decreased with an interval of 0.05. The XRD diffraction patterns measured demonstrated the ability to specifically control the ligand ratio using mechanochemical methods, and compared with the simulated data, they showed good fit.

[0115] Throughout this specification, reference to terms such as "one embodiment," "some embodiments," "illustrative embodiments," "examples," "specific examples," or "some examples" means that a specific feature, structure, material, or characteristic described in conjunction with that embodiment or example is included in at least one embodiment or example of the present invention. In this specification, illustrative uses of the above terms do not necessarily refer to the same embodiment or example. Furthermore, the specific features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.

[0116] While embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that various changes, modifications, substitutions, and variations may be made to the embodiments without departing from the principles and spirit of the invention, and that the scope of the invention is defined by the claims and their equivalents.

Claims

1. An oxide perovskite and porous glass composite material, characterized in that: include: oxide perovskites; A metal organic framework material (MOF), wherein the MOF encapsulates the oxide perovskite.

2. The oxide perovskite and porous glass composite material according to claim 1, characterized in that: The MOF is a zeolitic imidazolate framework material (ZIF).

3. The oxide perovskite and porous glass composite material according to claim 2, characterized in that: The MOF is selected from one or more of ZIF-4, ZIF-8, ZIF-62, and ZIF-76.

4. The oxide perovskite and porous glass composite material according to claim 1, characterized in that: The oxide perovskite is doped with rare earth elements.

5. The oxide perovskite and porous glass composite material according to claim 4, characterized in that: The rare earth elements include one or more of europium, terbium, yttrium and erbium.

6. A method for manufacturing an oxide perovskite and porous glass composite material, characterized in that: The following steps are involved: S10: taking an appropriate proportion of perovskite precursor materials, dissolving them in a polar solvent, filtering the solution, and heating them at a certain temperature for a certain time to synthesize oxide perovskite crystals; S20: Dissolve zinc nitrate hexahydrate, imidazole (Im), and benzimidazole (BIm) in a polar solvent in an appropriate ratio, heat at a certain temperature for a certain time, and then cool to room temperature at a certain rate to obtain a MOF; S30: heating the MOF obtained in step S20 in a tube furnace from room temperature to a certain temperature, and then cooling to room temperature; S40: mixing the oxide perovskite crystals obtained in steps S10 and S30 and the MOF in a certain ratio and grinding them together so that the MOF wraps the oxide perovskite crystals to obtain an oxide perovskite and porous glass composite material; S50: placing the oxide perovskite and porous glass composite material obtained by the S40 step into a tubular furnace for heat treatment, and performing heat treatment at a certain heating rate under the protection of flowing inert gas; when the sample reaches the specified temperature, immediately taking the entire tubular furnace out of the furnace, and quenching it directly by immersing it in liquid nitrogen under the protection of inert gas.

7. The method for manufacturing an oxide perovskite and porous glass composite material according to claim 6, wherein: The S10 further includes the following steps: washing the oxide perovskite solution after heating with methanol several times, and then drying it in a vacuum oven for a certain period of time to synthesize the oxide perovskite crystal; And / or the S20 further includes the following steps: washing the obtained MOF with methanol several times, then drying and heating it in an oven at a certain temperature for a certain time, and taking out the MOF for standby use.

8. The method for manufacturing an oxide perovskite and porous glass composite material according to claim 6, wherein: The polar solvent in step S10 and / or step S20 is N,N-dimethylformamide (DMF).

9. The method for manufacturing an oxide perovskite and porous glass composite material according to claim 6, wherein: In the step S30, the MOF is ZIF-62.

10. The method for manufacturing an oxide perovskite and porous glass composite material according to claim 6, wherein: In the step S40, the oxide perovskite crystals and MOF are ground by ball milling.

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