Fibrous mesoporous silica perovskite composite material and preparation method thereof

Abstract

The application discloses a fibrous mesoporous silica perovskite composite material and a preparation method thereof. The composite material comprises fibrous mesoporous silica and perovskite quantum dots which are in situ grown and uniformly distributed in the pores of the fibrous mesoporous silica. The fibrous mesoporous silica has a plurality of pores which are parallel to each other but not interconnected, and the pores are through holes along the length direction of the fibrous mesoporous silica. The molecular formula of the perovskite quantum dots is CsPbX3, and X is selected from halogens. The fibrous mesoporous silica perovskite composite material has a novel microstructure, especially excellent photothermal oxygen stability, and is expected to have a deep application prospect in the fields of photoelectric detection, solar cells, LEDs and the like.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of perovskite materials, and particularly relates to a fibrous mesoporous silica perovskite composite material and a preparation method thereof. BACKGROUND

[0002] In recent years, all-inorganic CsPbBr3 perovskite quantum dots have attracted more and more attention in LED devices, photodetectors, solar cells and other aspects due to their high color saturation, adjustable optical band gap and high quantum efficiency. However, due to the low lattice energy of CsPbBr3 and the strong ionicity of the crystal, the stability is the most prominent disadvantage. Their luminescence is sensitive to humidity, temperature and light, which easily causes luminescence quenching. When they are applied to LED devices, the generated heat effect will also cause fluorescence quenching; in addition, ion exchange easily occurs between different quantum dots, which causes the shift of their luminescence peak and affects the luminescence quality. Therefore, improving the stability of all-inorganic perovskite quantum dot materials and avoiding ion exchange between CsPbX3 quantum dots in device applications are the hot and difficult points in the field.

[0003] Mesoporous silica is a pore material with a connected network pore structure and a large specific surface area. Compared with an organic matrix, mesoporous silica has better chemical stability; compared with other inorganic matrices, mesoporous silica has better light transmittance and processing performance and can be processed into any shape such as a sheet, a fiber, a powder and the like. By introducing CsPbBr3 quantum dots into the pore channel of mesoporous silica, the space confinement effect of the pore channel is utilized to hinder water molecules from entering the pore channel and improve the stability of the CsPbBr3 quantum dots in the environment; and the nanopore channel can well disperse the CsPbX3 quantum dots, thereby reducing the agglomeration of the quantum dots during LED device packaging. Therefore, the preparation of mesoporous silica perovskite composite material has very important significance.

[0004] A mesoporous SiO2 perovskite quantum dot preparation method is disclosed in the literature Dirin D N, Protesescu L, Trummer D, et al. Harnessing Defect-Tolerance at the Nanoscale: Highly Luminescent Lead Halide Perovskite Nanocrystals in Mesoporous Silica Matrixes [J]. Nano Letters, 2016: 5866-5874. Commercially available mesoporous silica (spherical) is impregnated with an excess of concentrated precursor solution relative to the pore volume, and stirred in an inert gas at room temperature for 10 minutes to obtain a CsPbBr3 mesoporous silica perovskite composite with a size of 2.5-7 nm. However, since the commercially available mesoporous silica is difficult to control the pore size and overall morphology of the silica, the size of the perovskite quantum dots generated by the precursor impregnation method is also uneven.

[0005] In the literature Wang H C, Lin S Y, Tang A C, et al. Mesoporous Silica Particles Integrated with All-Inorganic CsPbBr3 Perovskite Quantum-Dot Nanocomposites (MP-PQDs) with High Stability and Wide Color Gamut Used for Backlight Display [J]. Angewandte Chemie International Edition, 2016, commercially available mesoporous silica (spherical) is simply impregnated with a CsPbX3 colloidal solution to prepare a mesoporous silica perovskite quantum dot composite. However, this method can only enter perovskite quantum dots of a specific size, resulting in a large portion of the pores being empty and containing fewer perovskites. And since it is a simple impregnation method, the perovskite quantum dots are easy to fall off from the mesoporous silica pores.

[0006] How to prepare a composite material with adjustable morphology and size, more accommodation, more uniform distribution and more stable combination of CsPbBr3 perovskite quantum dots is of great significance for the application of CsPbBr3 in LED and other optoelectronic devices. SUMMARY

[0007] In view of the deficiencies of the prior art, the application discloses a fibrous mesoporous silica perovskite composite material, the composite material has novel micro-morphology, the specific morphology can improve the photo-thermal oxygen stability of perovskite quantum dots, improve the agglomeration phenomenon of perovskite quantum dots, and is expected to be deeply applied in the fields of photoelectric detection, solar cells, LEDs and the like.

[0008] The specific technical scheme is as follows:

[0009] A fibrous mesoporous silica perovskite composite material, comprising fibrous mesoporous silica and perovskite quantum dots which are in situ grown and uniformly distributed in the pore channels of the fibrous mesoporous silica.

[0010] The fibrous mesoporous silica has a plurality of pore channels which are parallel to each other but not interconnected, and the pore channels are through holes along the length direction of the fibrous mesoporous silica.

[0011] The molecular formula of the perovskite quantum dots is CsPbX3, and X is selected from halogens.

[0012] The application further discloses a preparation method of the fibrous mesoporous silica perovskite composite material.

[0013] (1) a silicon source precursor and a pore-forming agent are fully hydrolyzed under an acidic condition, then a crystallization reaction is performed, and then high-temperature calcination is performed to obtain mesoporous silica;

[0014] The pore-forming agent is selected from polyethylene oxide-polypropylene oxide-polyethylene oxide triblock copolymer.

[0015] (2) a cesium precursor, oleic acid and octadecene are mixed until completely dissolved to obtain solution I, a lead halide, oleic acid, oleylamine and octadecene are mixed until completely dissolved, and then the mesoporous silica prepared in step (1) is added to obtain solution II;

[0016] (3) solution II is quickly injected into solution I, and the fibrous mesoporous silica perovskite composite material is obtained after sufficient reaction.

[0017] The application adopts a two-step preparation method of traditional sol-gel method and in-situ thermal injection method to obtain the composite material with novel micro-morphology, the specific pore-forming agent is used in the sol-gel reaction, the mesoporous silica with fibrous shape and a plurality of pore channels which are parallel to each other but not interconnected can be prepared, and the size and order degree of the pore channels in the mesoporous silica can be regulated by regulating the reaction temperature, so that the photo-thermal oxygen stability of the finally prepared composite material can be controlled.

[0018] It is found through comparison experiments that if other pore-forming agents commonly used in the art (such as cetyltrimethylammonium bromide, tetradecyltrimethylammonium bromide, dodecyltrimethylammonium bromide) are used in the sol-gel reaction, the prepared mesoporous silica perovskite composite material will no longer be fibrous, and further stability tests find that the stability of the composite material also decreases significantly; if the crystallization temperature in the sol-gel reaction is too low, the prepared mesoporous silica perovskite composite material will also no longer be fibrous, and further stability tests find that the stability of the composite material also decreases significantly; the above conclusions all show that the excellent photo-thermal-oxygen stability of the composite material prepared in the application is closely related to the special fibrous micro-morphology of the mesoporous silica used.

[0019] Preferably,

[0020] The length of the fibrous mesoporous silica is 300-850 nm, the diameter is 30-90 nm, and the average diameter of the pores in the fibrous mesoporous silica is 3-9 nm.

[0021] The size of the perovskite quantum dots is 4-6 nm.

[0022] Further preferably,

[0023] The length of the fibrous mesoporous silica is 400-600 nm, the diameter is 40-80 nm, and the average diameter of the pores in the fibrous mesoporous silica is 6-8 nm.

[0024] The size of the perovskite quantum dots is 4-5 nm.

[0025] It is found through experiments that as the above parameters are continuously optimized, the photo-thermal-oxygen stability of the prepared fibrous mesoporous silica perovskite composite material increases accordingly.

[0026] In step (1),

[0027] Preferably, the silicon source precursor is selected from one or more of tetramethoxysilane, tetraethoxysilane, and tetrapropoxysilane; further preferably, it is tetraethoxysilane.

[0028] Preferably, the mass ratio of the pore-forming agent to the silicon source precursor is 1:(1.5-2.5); further preferably, it is 1:(1.8-2.0).

[0029] Preferably, the pH value of the acidic condition is 1-2; the acidic condition is adjusted by adding an acidic substance commonly used in the art.

[0030] The acidic substance includes hydrochloric acid, sulfuric acid, nitric acid, etc.

[0031] Preferably, the raw material solution is heated to ≥40℃ for sufficient hydrolysis; further preferably, 40-60℃.

[0032] Preferably, the temperature of the crystallization reaction is 85-125℃.

[0033] It has been found through experiments that the temperature of the crystallization reaction (hydrothermal reaction) directly affects the micro size of the fibrous mesoporous silica prepared; as the temperature of the crystallization reaction increases, the order degree of the fibrous mesoporous silica prepared decreases; and when the temperature of the crystallization reaction is low, the pore diameter produced is small.

[0034] In order to take into account the order degree and the size of the pore diameter, further preferably, the temperature of the crystallization reaction is 100℃; it has been found through experiments that the photothermal oxygen stability of the fibrous mesoporous silica perovskite composite material prepared at this temperature is optimal.

[0035] Preferably, the temperature of the high-temperature calcination is 400-700℃; further preferably, 500-600℃.

[0036] In step (2):

[0037] Preferably, the cesium precursor is selected from cesium carbonate and / or cesium acetate.

[0038] Preferably, in the solution I, the concentration of the cesium precursor is 0.02-0.04 mol / L; further preferably, 0.025-0.035 mol / L.

[0039] Preferably, the molar ratio of the cesium precursor to oleic acid is 1:(10-15).

[0040] Preferably, the cesium precursor, oleic acid and octadecene are heated to ≥100℃ for complete dissolution; further preferably, heated to 110-130℃.

[0041] In step (2):

[0042] Preferably, the halide of lead is selected from one or more of lead fluoride, lead chloride, lead bromide and lead iodide; further preferably, lead bromide.

[0043] Preferably, in the solution II, the concentration of the halide of lead is 0.02-0.04 mol / L; further preferably, 0.025-0.035 mol / L.

[0044] Preferably, the mass ratio of the halide of lead to mesoporous silica is 1:(0.7-2.2); further preferably, 1:(1-1.5).

[0045] Preferably, the molar ratio of the halide of lead to oleic acid, oleylamine is 1:(10-15):(10-15).

[0046] In step (3):

[0047] Preferably, solution II is heated to 185-195 DEG C and then quickly injected into solution I;

[0048] Preferably, the reaction time is 10-20 min.

[0049] It is found through experiments that the reaction time needs to be controlled accurately, and if the reaction time is too long, such as 40 min, the product prepared will no longer be CsPbX3.

[0050] Preferably, the volume ratio of solution I to solution II is 1:(10-15); further preferably 1:(11-13).

[0051] The fibrous mesoporous silica perovskite composite material prepared by the above method has excellent stability.

[0052] Compared with the prior art, the present application has the following beneficial effects:

[0053] The present application discloses a fibrous mesoporous silica perovskite composite material, which has a novel microstructure, and perovskite quantum dots are in-situ grown and uniformly distributed in the pore channels of the fibrous mesoporous silica.

[0054] The preparation method disclosed by the present application adopts a conventional sol-gel method combined with an in-situ hot injection method, and can realize the regulation of the pore channel diameter and order degree of the fibrous mesoporous silica through production process parameters, so as to regulate the photo-thermal-oxygen stability of the finally prepared composite material. BRIEF DESCRIPTION OF DRAWINGS

[0055] Figure 1 The XRD pattern of the fibrous mesoporous silica perovskite composite material prepared in Example 1;

[0056] Figure 2 The SEM image of the fibrous mesoporous silica perovskite composite material prepared in Example 1;

[0057] Figure 3 The TEM image of the fibrous mesoporous silica perovskite composite material prepared in Example 1;

[0058] Figure 4 The HRTEM image of the fibrous mesoporous silica perovskite composite material prepared in Example 1;

[0059] Figure 5 Pore diameter distribution of the fibrous mesoporous silica perovskite composite prepared in Example 1;

[0060] Figure 6 Small angle X-ray scattering (SAXS) pattern of the fibrous mesoporous silica perovskite composite prepared in Example 1, 2 to 4, respectively;

[0061] Figure 7 Luminescence intensity change curve with time of the fibrous mesoporous silica perovskite composite prepared in Example 1;

[0062] Figure 8 Luminescence intensity change curve with temperature of the fibrous mesoporous silica perovskite composite prepared in Example 1;

[0063] Figure 9 SEM image of the product prepared in Comparative Example 1;

[0064] Figure 10 Luminescence intensity change curve with time of the product prepared in Comparative Example 1;

[0065] Figure 11 TEM image of the product prepared in Comparative Example 2;

[0066] Figure 12 XRD pattern of the product prepared in Comparative Example 3;

[0067] Figure 13 TEM image of the product prepared in Comparative Example 4;

[0068] Figure 14 Luminescence intensity change curve with time of the product prepared in Comparative Example 4;

[0069] Figure 15 TEM image of the fibrous mesoporous silica perovskite composite prepared in Example 2;

[0070] Figure 16 Pore diameter distribution of the fibrous mesoporous silica perovskite composite prepared in Example 3;

[0071] Figure 17 Luminescence spectrum change curve with time of the fibrous mesoporous silica perovskite composite prepared in Example 3;

[0072] Figure 18 Pore diameter distribution of the fibrous mesoporous silica perovskite composite prepared in Example 4;

[0073] Figure 19The luminescence spectrum of the fibrous mesoporous silica perovskite composite material prepared in Example 4 changes over time. DETAILED DESCRIPTION

[0074] In order to make the purposes, technical solutions and advantages of the embodiments of the present application clearer, the technical solutions in the embodiments of the present application will be described clearly and completely below. If specific conditions are not specified in the embodiments, conventional conditions or conditions recommended by manufacturers are adopted. If the manufacturers of reagents or instruments are not specified, they are all conventional products that can be purchased on the market.

[0075] The features and performances of the present application are further described in detail below in combination with the embodiments.

[0076] Example 1

[0077] (1) 2 g of polyethylene oxide-polypropylene oxide-polyethylene oxide triblock copolymer (P123) and 4.17 mL of tetraethoxysilane (TEOS, 3.9 g) were fully stirred in 15 mL of water, and 60 mL of an aqueous hydrochloric acid solution (2 mol / L) was used to adjust the pH to 1.5. After stirring for 24 h, the mixture was crystallized in an autoclave at 100℃ for 48 h, and then subjected to suction filtration, washing and drying. After high-temperature calcination at 550℃ for 6 h, a powder was obtained, which was mesoporous silica;

[0078] (2) 100 mg of cesium carbonate (0.3 mmol), 1 mL of oleic acid (3 mmol) and 10 mL of octadecene were fully reacted and dissolved under vacuum at 120℃ to obtain solution I;

[0079] (3) 138 mg (0.38 mmol) of lead bromide, 10 mL of octadecene, 1 mL of oleic acid (3 mmol), and 1 mL of oleylamine (3 mmol) were fully dissolved at 120℃, and then 200 mg of mesoporous silica was added. After being fully immersed for 60 min, solution II was obtained;

[0080] (4) 12 mL of solution II was warmed to 190℃, and 1 mL of solution I was quickly injected. After stirring at the same temperature for 10 min, a reaction solution was obtained. Finally, the final product was obtained after centrifugation, separation and washing, which was recorded as CsPbBr3@SiO2 composite material.

[0081] Figure 1 The XRD pattern of the product prepared in this example was observed, and it was confirmed that the product was composed of CsPbBr3 and SiO2.

[0082] Figure 2 The SEM pattern of the product prepared in this example was observed, and it was found that fibrous CsPbBr3@SiO2 composite material was prepared, with a length of 400-600 nm and a diameter of 40-80 nm.

[0083] Figure 3 The TEM image of the product prepared in the present example shows that the channel diameter of the prepared CsPbBr3@SiO2 composite material is about 7 nm, and the CsPbBr3 perovskite quantum dots are uniformly distributed in the inside.

[0084] Figure 4 The HRTEM image of the product prepared in the present example shows that the size of the perovskite quantum dots in the prepared CsPbBr3@SiO2 composite material is about 4-5 nm, and the perovskite quantum dots are uniformly distributed in the channels.

[0085] The pore diameter distribution graph of the product prepared in the present example was tested by nitrogen adsorption method, and as shown in Figure 5 , it was found that the channel diameter distribution was concentrated and mainly distributed in 6-8 nm.

[0086] Figure 6 The SAXS spectrum of the product prepared in the present example shows that the product prepared in the present example has good order. The SAXS spectra of the products prepared in examples 3 and 4 are also given in the figure, and it is found by comparison that the order of the prepared product decreases with the increase of the crystallization temperature.

[0087] Performance test

[0088] 1. Light stability test:

[0089] The CsPbBr3@SiO2 composite material prepared in the present example was placed at room temperature 25℃ and humidity 40% for 9 days, and then tested by FLS1000 spectrometer, with excitation light set to 365 nm, incident light grating set to 1, and emission light grating set to 0.7.

[0090] Figure 7 The light intensity of the product prepared in the present example changes with time, and it can be seen that the composite material shows high spectral stability, and the light intensity still maintains 91.6% after one week. The specific values are listed in Table 1 below.

[0091] Table 1

[0092]

[0093] 2. Thermal stability test:

[0094] The CsPbBr3@SiO2 composite material prepared in the present example was tested by FLS1000 for variable temperature spectrum, with incident light grating set to 0.5, emission light grating set to 0.5, excitation light wavelength 365 nm, and heating rate 10 K / min, and liquid nitrogen was used for cooling.

[0095] Figure 8The luminescence intensity of the product prepared in this example as a function of temperature was plotted, and the temperature was gradually increased in the direction of the arrow, with the specific values listed in Table 2 below. It was observed that at 100°C, the luminescence intensity was still 50% of the initial value, which was better than the 10% reported in the literature.

[0096] Table 2

[0097]

[0098] Comparative Example 1

[0099] The preparation process was basically the same as in Example 1, except that the crystallization temperature in step (1) was replaced by 70°C.

[0100] Figure 9 The SEM image of the product prepared in this comparative example was found to be short rod-shaped.

[0101] Figure 10 The luminescence intensity of the product prepared in this comparative example as a function of time was plotted, and it could be seen that the spectral stability of the composite material was poor, much lower than that of the composite material prepared in Example 1. The specific values are listed in Table 3 below.

[0102] Table 3

[0103]

[0104] Comparative Example 2

[0105] The preparation process was basically the same as in Example 1, except that the crystallization temperature in step (1) was replaced by 150°C.

[0106] Figure 11 The TEM image of the product prepared in this comparative example was found to have a large number of perovskite quantum dots growing outside the pores, which may be due to the fact that the crystallization temperature was too high, resulting in a smaller pore size of the mesoporous silica prepared.

[0107] Comparative Example 3

[0108] The preparation process was basically the same as in Example 1, except that in step (4):

[0109] Solution II was warmed to 190°C, and 1 mL of solution I was quickly injected, and then stirred at the same temperature for 40 min to obtain the reaction solution.

[0110] Figure 12 The XRD pattern of the product prepared in this comparative example was tested, and the composition of the product was found to be CsPb2Br5.

[0111] Comparative Example 4

[0112] (1) 2 g of cetyltrimethylammonium bromide (CTAB) and 4.17 ml of TEOS were mixed in 480 ml of water, and after stirring for 2 h with pH adjusted to 11 by 1 mol / L NaOH, the mixture was filtered, washed and dried, and then mesoporous silica was obtained by adding at 550°C for 6 h;

[0113] (2) - (4) were the same as in Example 1.

[0114] Figure 13 A TEM image of the product prepared in this comparative example was prepared, and it was found that the prepared composite material was spherical.

[0115] Figure 14 A plot of the luminescence intensity of the product prepared in this comparative example as a function of time was prepared, and the stability was still inferior to that of Example 1. The specific values are listed in Table 4 below.

[0116] Table 4

[0117]

[0118] Comparative Examples 5 - 6

[0119] The preparation process was basically the same as in Comparative Example 4, except that in step (1) the CTAB was replaced by equal amounts of tetradecyltrimethylammonium bromide and dodecyltrimethylammonium bromide, respectively.

[0120] TEM tests showed that the composite materials prepared in Comparative Examples 5 and 6 were also spherical.

[0121] Example 2

[0122] The preparation process was basically the same as in Example 1, except that the stirring time in step (4) was replaced by 20 min.

[0123] Figure 15 A TEM image of the product prepared in this example was prepared, and it was found that the morphology and size were basically the same as in Example 1.

[0124] Example 3

[0125] The preparation process was basically the same as in Example 1, except that the crystallization temperature in step (1) was replaced by 125°C.

[0126] Figure 16 A pore diameter distribution plot of the product prepared in this example was prepared, and it was found that the pore diameter distribution was relatively concentrated, mainly distributed in the range of 6 - 7.3 nm.

[0127] Figure 17 A plot of the luminescence spectrum of the product prepared in this example as a function of time was prepared, and it was found that the luminescence spectrum was relatively stable. The specific values are listed in Table 5 below.

[0128] Table 5

[0129]

[0130] Example 4

[0131] The preparation process is basically the same as that in Example 1, except that the crystallization temperature in step (1) is replaced by 85°C.

[0132] Figure 18 The pore diameter distribution graph of the product prepared in this example shows that the pore diameter distribution is relatively concentrated, mainly distributed in 3-6 nm.

[0133] Figure 19 The luminescence spectrum of the product prepared in this example shows high spectral stability over time. The specific values are listed in Table 6 below.

[0134] Table 6

[0135]

[0136] The above discloses the preferred embodiments, but the protection scope of the present application is not limited thereto, and those skilled in the art can easily understand the spirit of the present application according to the above embodiments, and make different inferences and changes, as long as they do not deviate from the spirit of the present application, they are within the protection scope of the present application.

Claims

1. A fibrous mesoporous silica perovskite composite material, characterized in that, Includes fibrous mesoporous silica and perovskite quantum dots that are grown in situ and uniformly distributed inside the pores of the fibrous mesoporous silica. The fibrous mesoporous silica has a number of parallel but non-interconnected channels, which are through holes along the length of the fibrous mesoporous silica. The fibrous mesoporous silica has a length of 300-850 nm and a diameter of 30-90 nm, and the average diameter of several channels in the fibrous mesoporous silica is 3-9 nm; the molecular formula of the perovskite quantum dots is CsPbX3, where X is selected from halogens. The perovskite quantum dots have a size of 4-6 nm.

2. The fibrous mesoporous silica perovskite composite material according to claim 1, characterized in that: The fibrous mesoporous silica has a length of 400~600 nm and a diameter of 40~80 nm, and the average diameter of a plurality of channels in the fibrous mesoporous silica is 6~8 nm. The size of the perovskite quantum dots is 4~5 nm.

3. A method for preparing a fibrous mesoporous silica perovskite composite material according to any one of claims 1 to 2, characterized in that, Includes the following steps: (1) The silicon source precursor and pore-forming agent are fully hydrolyzed under acidic conditions and then crystallized, and then calcined at high temperature to obtain mesoporous silicon dioxide; The pore-forming agent is selected from polyethylene oxide-polypropylene oxide-polyethylene oxide triblock copolymer; The temperature of the crystallization reaction in step (1) is 85~125℃; (2) Mix the cesium precursor, oleic acid and octadecene until completely dissolved to obtain solution I. Mix the lead halide, oleic acid, oleylamine and octadecene until completely dissolved, and then add the mesoporous silica prepared in step (1) to obtain solution II. (3) Solution II is rapidly injected into solution I, and after sufficient reaction, the fibrous mesoporous silica perovskite composite material is obtained; The reaction time in step (3) is 10-20 minutes.

4. The method for preparing the fibrous mesoporous silica perovskite composite material according to claim 3, characterized in that, In step (1): The silicon source precursor is selected from one or more of tetramethoxysilane, tetraethoxysilane, and tetrapropoxysilane; The mass ratio of pore-forming agent to silicon source precursor is 1:(1.5~2.5); The pH value of the acidic conditions is 1~2; The high-temperature calcination temperature is 400~700℃.

5. The method for preparing the fibrous mesoporous silica perovskite composite material according to claim 3, characterized in that, In step (2): The cesium precursor is selected from cesium carbonate and / or cesium acetate; In solution I, the concentration of the cesium precursor is 0.02~0.04 mol / L; The molar ratio of cesium precursor to oleic acid is 1:(10~15).

6. The method for preparing the fibrous mesoporous silica perovskite composite material according to claim 3, characterized in that, In step (2): The lead halide is selected from one or more of lead fluoride, lead chloride, lead bromide, and lead iodide; In solution II, the concentration of lead halide is 0.02~0.04 mol / L; The mass ratio of lead halide to mesoporous silica is 1:(0.7~2.2). The molar ratio of lead halide to oleic acid and oleylamine is 1:(10~15):(10~15).

7. The method for preparing the fibrous mesoporous silica perovskite composite material according to claim 3, characterized in that, In step (3): First, heat solution II to 185~195℃ and then quickly inject it into solution I.

8. The method for preparing the fibrous mesoporous silica perovskite composite material according to claim 3, characterized in that, In step (3), the volume ratio of solution I to solution II is 1:(10~15).

9. The method for preparing the fibrous mesoporous silica perovskite composite material according to any one of claims 3 to 8, characterized in that, The temperature of the crystallization reaction in step (1) is 100℃.

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