Aggregation-induced emission material with high fluorescence quantum yield as well as preparation method and application of aggregation-induced emission material

Abstract

The invention discloses an aggregation-induced emission material with high fluorescence quantum yield as well as a preparation method and application thereof, and relates to the technical field of preparation of fluorescent solar condensers. The invention provides an aggregation-induced emission material with high fluorescence quantum yield, and the aggregation-induced emission material has high red light quantum yield, and can effectively overcome the problem of low efficiency of the existing fluorescent solar concentrator. A fluorescent solar concentrator prepared on the basis of the aggregation-induced emission material with high fluorescence quantum yield not only can effectively shield harmful ultraviolet rays, but also can increase the density of red light which is crucial to plant growth, so that the plant growth is remarkably promoted, and the yield increasing effect is realized.

Description

Technical Field

[0001] The present invention relates to the technical field of fluorescent solar concentrator preparation, and in particular to a high fluorescence quantum yield aggregation-induced luminescence material, a preparation method and application thereof. Background Art

[0002] With the rapid advancement of society, the demand for energy in the industrial sector has skyrocketed. At the same time, ecological and environmental issues have become increasingly prominent, making it difficult for traditional fossil energy to meet the strategic requirements of sustainable development. In the vast field of exploring renewable energy, solar energy, with its vast reserves, wide distribution range, and environmentally friendly properties, has become a highly promising long-term energy solution.

[0003] Solar energy can be utilized in a variety of ways, with photovoltaic and photothermal conversion being two of its core applications. Photovoltaic conversion, particularly through solar photovoltaic technology, has become a highly efficient method for converting solar energy into electricity, demonstrating positive contributions to alleviating energy shortages, improving environmental quality, and addressing climate change. However, solar photovoltaic power generation currently faces the dual challenges of high costs and a need to improve photovoltaic conversion efficiency.

[0004] To address these challenges, researchers have proposed a concentrating strategy, which uses optical methods to concentrate sunlight from a large area onto a small solar panel, thereby increasing the light intensity per unit area and thereby improving the energy conversion efficiency of the solar cell. This strategy is expected to not only significantly improve the utilization rate of solar cells, but also significantly reduce the overall cost of solar photovoltaic power generation, opening up new avenues for the large-scale commercial application of solar energy. The fluorescence quantum yield of the fluorescent material itself often plays a significant role in the efficiency of fluorescent solar concentrators.

[0005] Typically, molecules that emit red light (emission wavelength greater than 600nm) have low fluorescence quantum efficiency and severe self-absorption, making fluorescent solar concentrators emitting red light or longer wavelengths inefficient. By optimizing the molecular structure and the configuration and conformation of the aggregated state, the aggregate material can be given weak self-absorption and high fluorescence quantum efficiency, thereby preparing a fluorescent solar concentrator with both low and high efficiency. Furthermore, fluorescent power generation glass has the added value of converting the sunlight spectrum, such as shielding ultraviolet rays and increasing the density of certain wavelengths. Expanding its added value in terms of power generation and energy conservation is crucial to building multi-dimensional benefits.

[0006] Fluorescent solar concentrators (LSCs) are simple devices for light energy absorption, conversion, and concentration. They consist of a transparent thin plate with high refractive index characteristics, in which a low concentration of luminophores (luminescent substances or fluorescent substances) are embedded. The luminophores in the LSC absorb most of the light in the solar radiation spectrum and then re-emit it at longer wavelengths through the process of photoluminescence (PL). Photoluminescence is a photochemical process that occurs in many optical and semiconductor organic and inorganic materials. In addition, in addition to containing fluorescent emitters in the main matrix, this system can also convert fluorescent photons into electrical energy, thereby improving the photoelectric conversion efficiency of solar cells per unit area. Fluorescent power generation glass is a product based on fluorescent solar concentrator technology, including glass packaging technology and circuit technology corresponding to photovoltaic cells, etc., which is the basis for realizing the application of the technology in daily life. Summary of the Invention

[0007] An object of the present invention is to provide a material with high fluorescence quantum yield for aggregation-induced emission and its preparation method and application, so as to overcome the problem of low efficiency of existing fluorescent solar concentrators, especially the problem of low red light fluorescence quantum efficiency.

[0008] To achieve the above object, the present invention provides the following solutions:

[0009] One object of the present invention: to provide a material for aggregation-induced emission having a general formula structure shown in Formula I:

[0010]

[0011] Among them, A is selected from

[0012] R is independently selected from H or -OCH3.

[0013] The specific structure of the above compound of the present invention is as follows:

[0014]

[0015] Another object of the present invention: to provide a preparation method of the above material for aggregation-induced emission, including the following steps:

[0016] In a protective atmosphere, a compound containing group A is subjected to a Suziki coupling reaction with a compound containing group (tetraphenylethylene compound), and the reaction product is extracted and dried to obtain the material for aggregation-induced emission;

[0017] Among them, A is selected from

[0018] R is independently selected from H or -OCH3.

[0019] As a further preference of the present invention, the compound containing group A is 4,7-dibromo-2,1,3-benzothiadiazole or 4,9-dibromonaphthothiadiazole; the compound containing

[0020] group is [1-(4-borate phenyl)-1,2,2-triphenyl]ethylene or (4-(2,2-bis(4-methoxyphenyl)-1-phenylethenyl)phenyl)boronic acid.

[0021] The third object of the present invention is to provide an application of the above aggregation-induced emission material in the preparation of fluorescent power generation glass or fluorescent solar concentrator.

[0022] The fourth object of the present invention is to provide a fluorescent power generation glass using the above aggregation-induced emission material as a fluorescent material.

[0023] The fifth object of the present invention is to provide a preparation method of the above fluorescent power generation glass, comprising the following steps:

[0024] Mix the aggregation-induced emission material with a film material, coat the obtained mixture on a glass substrate, and dry it to obtain the fluorescent power generation glass.

[0025] The sixth object of the present invention is to provide a fluorescent solar concentrator comprising the above aggregation-induced emission material or the above fluorescent power generation glass.

[0026] The fluorescent solar concentrator can be further circuit-connected to a storage battery to store the electric energy generated by the fluorescent solar concentrator.

[0027] The seventh technical solution of the present invention is to provide an application of the above fluorescent power generation glass or fluorescent solar concentrator in greenhouse cultivation.

[0028] By designing the absorption and emission spectra of the compound, the present invention successfully develops an aggregation-induced emission (AIE) material with a high fluorescence quantum yield. This material exhibits excellent luminescence performance in the red light band and has a significantly higher red light quantum yield than traditional fluorescent materials. The fluorescent solar concentrator (FSC) prepared based on this high-performance aggregation-induced emission material not only has high energy conversion efficiency but also shows unique additional value in the fields of agriculture and environmental protection:

[0029] (1) High fluorescence quantum yield

[0030] By modifying the electron donor and acceptor, the molecular configuration and conformation of the aggregated state and the emission wavelength are regulated. The aggregation-induced emission material exhibits significantly enhanced fluorescence intensity in the aggregated state, avoiding the fluorescence quenching phenomenon caused by aggregation of traditional fluorescent materials, especially having a high quantum yield in the red light band.

[0031] (2) Shield harmful ultraviolet rays

[0032] The fluorescent solar concentrator prepared based on the aggregation-induced emission material of the present invention can effectively absorb and shield ultraviolet rays (UV) harmful to organisms, thereby protecting plants from damage by ultraviolet radiation. This characteristic is particularly important for greenhouse agriculture, indoor cultivation, and other light-sensitive environments.

[0033] (3) Increase the red light density

[0034] Red light is one of the most effective spectra in plant photosynthesis and plays a key role in promoting plant growth and increasing yield. The fluorescent solar concentrator based on the aggregation-induced emission material of the present invention can convert invisible light or low-efficiency spectra into red light and significantly increase its density, thereby optimizing the photosynthesis conditions of plants, significantly promoting plant growth, and achieving the effect of increasing production.

[0035] (4) Energy conservation and environmental protection

[0036] The fluorescent solar concentrator based on the aggregation-induced emission material of the present invention can efficiently convert solar energy into electrical energy, further reducing energy consumption and achieving the goal of green environmental protection. At the same time, the intelligent design based on this can combine sensor technology to real-time monitor environmental parameters such as light intensity and temperature, providing a precise control solution for modern agriculture.

[0037] The synthesis steps of the organic small molecules of the present invention are simple. It can not only be prepared efficiently and in large quantities, but also the obtained aggregation-induced emission material has high fluorescence quantum efficiency, wide visible light absorption spectrum, and excellent anti-photobleaching property. Moreover, the fluorescent power generation glass has the function of converting the sunlight spectrum, such as shielding ultraviolet rays and increasing the density of some wavelength spectra.

[0038] The optical solar concentrator based on the aggregation-induced emission material of the present invention can be used for greenhouse plant cultivation, not only reducing the inhibitory effect of ultraviolet light on crop growth, but also the red fluorescence emission can increase the yield of crops, and the electrical energy generated according to the circuit design can be used for ventilation and temperature and humidity monitoring in the greenhouse, etc., contributing to the development of intelligent and clean agriculture.

[0039] The present invention discloses the following technical effects:

[0040] By designing the absorption and emission spectra of compounds, the present invention provides an aggregation-induced emission material with a high fluorescence quantum yield, and this aggregation-induced emission material has a high red light quantum yield.

[0041] The fluorescence solar concentrator prepared based on this aggregation-induced emission material with a high fluorescence quantum yield can not only effectively shield harmful ultraviolet rays, but also increase the red light density crucial for plant growth, thereby significantly promoting plant growth and achieving an increased yield effect. BRIEF DESCRIPTION OF THE DRAWINGS

[0042] In order to more clearly illustrate the technical solutions in the embodiments of the present invention or the prior art, the following will briefly introduce the drawings required to be used in the embodiments. Obviously, the drawings described below are only some embodiments of the present invention. For those of ordinary skill in the art, without creative efforts, other drawings can be obtained based on these drawings.

[0043] Figure 1 It is the absorption and emission spectra of the aggregation-induced emission material B3 compound prepared in Example 3 of the present invention and the B4 compound prepared in Example 4.

[0044] Figure 2 It is the J-V characteristic curve of the fluorescence solar concentrator prepared based on compounds B1 and B2 in Examples 9 and 10 of the present invention.

[0045] Figure 3 It is the actual picture of the roots and leaves of lettuce planted in the greenhouses built with the fluorescence solar concentrators in the experimental group and the control group.

[0046] Figure 4 It is the light intensity distribution of different bands in the greenhouses built with the fluorescence solar concentrators in the experimental group B3 and the control group.

[0047] Figure 5 It is the change of the fluorescence quantum yield with time of the fluorescence solar concentrator prepared based on compound B3 in Example 11 of the present invention under UV irradiation.

[0048] Figure 6 It is the fresh weight comparison of lettuce planted in the greenhouses built with the fluorescence solar concentrators in the experimental group and the control group. DETAILED DESCRIPTION OF THE INVENTION

[0049] Now, various exemplary embodiments of the present invention will be described in detail. This detailed description should not be considered as a limitation of the present invention, but should be understood as a more detailed description of certain aspects, characteristics, and implementation schemes of the present invention.

[0050] It should be understood that the terms used in the present invention are only for describing specific embodiments and are not intended to limit the present invention. Additionally, for the numerical ranges in the present invention, it should be understood that each intermediate value between the upper and lower limits of the range is also specifically disclosed. Any intermediate value within any stated value or stated range, as well as each smaller range between any other stated value or intermediate value within the stated range, is also included in the present invention. The upper and lower limits of these smaller ranges may be independently included or excluded from the range.

[0051] Unless otherwise specified, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention pertains. Although the present invention only describes preferred methods and materials, any methods and materials similar or equivalent to those described herein can also be used in the implementation or testing of the present invention. All documents mentioned in this specification are incorporated by reference to disclose and describe the methods and / or materials related to the said documents. In case of conflict with any incorporated document, the content of this specification shall prevail.

[0052] Without departing from the scope or spirit of the present invention, various improvements and changes can be made to the specific embodiments of the present invention specification, which are obvious to those skilled in the art. Other embodiments obtained from the specification of the present invention are obvious to those skilled in the art. The specification and examples of the present invention are merely exemplary.

[0053] Regarding the use of "comprising", "including", "having", "containing", etc. herein, they are all open-ended terms, meaning including but not limited to.

[0054] It should be noted that those aspects not described in detail in the present invention are all conventional operating means in the art and are not the focus of the present invention.

[0055] Example 1 Preparation of Compound B1

[0056] Under a nitrogen atmosphere, [1-(4-boronate phenyl)-1,2,2-triphenyl]ethylene (4 mmol), 4,7-dibromo-2,1,3-benzothiadiazole (2 mmol), and potassium carbonate (8 mmol) were added to a 20 mL mixed solution of toluene and water. The mixture was reacted at 100 °C for 12 h, and the reaction progress was monitored using a TLC plate. After the reaction was completed, the reaction solution was cooled to room temperature, and the resulting crude product was extracted with a water and dichloromethane system, and then the solvent was removed by distillation under reduced pressure. The crude product was separated by column chromatography using dichloromethane and petroleum ether (volume ratio 1:1) to obtain yellow powder B1 (yield 95%).

[0057] Example 2 Preparation of Compound B2

[0058] In an N2 atmosphere, (4-(2,2-bis(4-methoxyphenyl)-1-phenylethenyl)phenyl)boronic acid (4 mmol), 4,7-dibromo-2,1,3-benzothiadiazole (2 mmol), and potassium carbonate (8 mmol) were added to a 20 mL mixed solution of toluene and water. The mixed solution was reacted at 100 °C for 12 h, and the reaction progress was monitored using a TLC plate. After the reaction was completed, the reaction solution was cooled to room temperature, and the resulting crude product was extracted with a water and dichloromethane system, and then the solvent was removed by distillation under reduced pressure. The crude product was separated by column chromatography using dichloromethane and petroleum ether (volume ratio 1:1) to obtain yellow powder B1 (yield 85%).

[0059] Preparation of Compound B3 in Example 3

[0060] In an N2 atmosphere, [1-(4-borate phenyl)-1,2,2-triphenyl]ethylene (4 mmol), 4,9-dibromonaphthothiadiazole (2 mmol), and potassium carbonate (8 mmol) were added to a 20 mL mixed solution of toluene and water. The mixed solution was reacted at 100 °C for 12 h, and the reaction progress was monitored using a TLC plate. After the reaction was completed, the reaction solution was cooled to room temperature, and the resulting crude product was extracted with a water and dichloromethane system, and then the solvent was removed by distillation under reduced pressure. The crude product was separated by column chromatography using dichloromethane and petroleum ether (volume ratio 1:1) to obtain orange powder B3 (yield 93%).

[0061] Preparation of Compound B4 in Example 4

[0062] In an N2 atmosphere, (4-(2,2-bis(4-methoxyphenyl)-1-phenylethenyl)phenyl)boronic acid (4 mmol), 4,9-dibromonaphthothiadiazole (2 mmol), and potassium carbonate (8 mmol) were added to a 20 mL mixed solution of toluene and water. The resulting mixed solution was reacted at 100 °C for 12 h, and the reaction progress was monitored using a TLC plate. After the reaction was completed, the reaction solution was cooled to room temperature, and the resulting crude product was extracted with a water and dichloromethane system, and then the solvent was removed by distillation under reduced pressure. The crude product was separated by column chromatography using dichloromethane and petroleum ether (volume ratio 1:1) to obtain yellow powder B4 (yield 65%).

[0063] Figure 1 Absorption and emission spectra of the aggregation-induced emission materials B3 and B4 compounds prepared in Examples 3 and 4 of the present invention. It can be seen that the compounds of the present invention can effectively emit red light that is beneficial to plant growth and can convert ultraviolet light into orange-red light.

[0064] [[ID=]19]Example 5 Preparation of a Fluorescent Power Generation Glass

[0065] Dissolve 5 g of polymethyl methacrylate in toluene and stir to completely dissolve it to prepare a 20 wt% (mass content of polymethyl methacrylate) solution. Then add the prepared B1 compound to the above solution and ultrasonicate for 20 min to completely remove the bubbles, and prepare a solution with a concentration of 3 wt% (mass content of B1 compound).

[0066] Use a coater to scrape the obtained solution onto the surface of a glass substrate, and place it in an 80 °C oven for solvent evaporation to form a film. The evaporation time is 48 h to obtain a fluorescence power generation glass with high fluorescence quantum yield and low loss (film thickness is 20 μm).

[0067] Example 6

[0068] The difference from Example 5 is only that the B1 compound is replaced with the B2 compound.

[0069] Example 7

[0070] The difference from Example 5 is only that the B1 compound is replaced with the B3 compound.

[0071] Example 8

[0072] The difference from Example 5 is only that the B1 compound is replaced with the B4 compound.

[0073] Example 9

[0074] Seal a monocrystalline silicon solar cell on the side of the fluorescence power generation glass prepared in Example 5 with NOV68 optical glue at the edge, and connect the solar panels in parallel to obtain a fluorescence solar concentrator.

[0075] Example 10

[0076] The difference from Example 9 is only that the fluorescence power generation glass prepared in Example 5 is replaced with the fluorescence power generation glass prepared in Example 6.

[0077] Example 11

[0078] The difference from Example 9 is only that the fluorescence power generation glass prepared in Example 5 is replaced with the fluorescence power generation glass obtained in Example 7.

[0079] Example 12

[0080] The difference from Example 9 is only that the fluorescence power generation glass prepared in Example 5 is replaced with the fluorescence power generation glass of Example 8.

[0081] Figure 2J-V characteristic curves of the fluorescent solar concentrators prepared based on Compounds B1 and B2 in Embodiments 9 and 10 of the present invention (labeled as B1 and B2). It can be seen that the fluorescent solar concentrators based on the compounds of the present invention have high photoelectric conversion efficiency.

[0082] Construction of a greenhouse based on a fluorescent solar concentrator and plant cultivation:

[0083] 1. Experimental grouping: An outdoor glass greenhouse experiment was conducted. The simulated greenhouse had a length of 40 cm, a width of 30 cm, and an area of 1200 cm 2 . The fluorescent solar concentrators prepared in Embodiments 11 and 12 were used to build greenhouses as the experimental groups (labeled as B3 and B4 respectively), and blank glass was used to build greenhouses of the same specifications as the control group (labeled as blank).

[0084] 2. Experimental crops: Lettuce (seeds purchased from a website).

[0085] 3. Experimental treatment: Four days after sowing, the seeds germinated and emerged. The seedlings were transplanted, with one seedling per pot, and placed under the simulated glass greenhouse. Four pots of seedlings with consistent growth and good health were planted in each greenhouse area, and the water and fertilizer management measures were carried out according to the conventional method.

[0086] 4. Statistical analysis of experimental results: The growth of plants was statistically analyzed 15 days after sowing. The growth trends of plants in the experimental group and the control group (including the size and area of roots, stems, and leaves) were compared, and the average values were taken.

[0087] 5. Analysis of experimental results: Compared with the control group, the leaf area of lettuce in the experimental group increased significantly, and the roots and stems became thicker, indicating that the greenhouse with the fluorescent solar concentrator prepared by the present invention can improve the utilization rate of sunlight by crops and enhance the photosynthetic ability of crops.

[0088] Figure 3 Actual photos of the roots and leaves of lettuce planted in the greenhouses built with the fluorescent solar concentrators in the experimental group and the control group.

[0089] The fluorescent solar concentrator prepared by the present invention can convert part of the ultraviolet light that is not conducive to plant growth into orange-red light absorbed and utilized by chlorophyll a, b, and carotenoids, improving the light quality of the transmitted light, promoting crop photosynthesis, and increasing the yield of agricultural crops.

[0090] Figure 4 Light intensity distribution of different wavelength bands in the greenhouses built with the fluorescent solar concentrators in the experimental group and the control group.

[0091] Figure 5 Variation of the fluorescence quantum yield of the fluorescent solar concentrator prepared based on Compound B3 in Embodiment 11 of the present invention with time under UV irradiation.

[0092] Figure 6 Comparison of the fresh weight of lettuce grown in the greenhouses built for the fluorescent solar concentrators in the experimental group and the control group.

[0093] The embodiments described above are only descriptions of the preferred embodiments of the present invention, and do not limit the scope of the present invention. Without departing from the design spirit of the present invention, various deformations and improvements made by those of ordinary skill in the art to the technical solutions of the present invention shall fall within the protection scope determined by the claims of the present invention.

Claims

1. An aggregation-induced emission material, characterized in that, Having the general formula structure shown in Formula I: Among them, A is selected from R is independently selected from H or -OCH3.

2. The preparation method of the aggregation-induced emission material according to claim 1, wherein Comprising the following steps: In a protective atmosphere, a compound containing group A is subjected to a Suzuki coupling reaction with a compound containing group, and the reaction product is extracted and dried to obtain the aggregation-induced emission material; Among them, A is selected from R is independently selected from H or -OCH3.

3. The preparation method according to claim 2, wherein, The compound containing group A is 4,7-dibromo-2,1,3-benzothiadiazole or 4,9-dibromonaphthothiadiazole; the compound containing group is [1-(4-borate phenyl)-1,2,2-triphenyl]ethylene or (4-(2,2-bis(4-methoxyphenyl)-1-phenylethenyl)phenyl)boronic acid.

4. The preparation method according to claim 2, characterized in that, The temperature of the Suzuki coupling reaction is 90 - 120 °C and the time is 12 h.

5. Use of the aggregation-induced emission material according to claim 1 in the preparation of fluorescent power generation glass or fluorescent solar concentrators.

6. A fluorescent power generation glass, characterized in that, Using the aggregation-induced emission material according to claim 1 as the fluorescent material.

7. The preparation method of the fluorescent power generation glass according to claim 6, characterized in that, Comprising the following steps: Mixing the aggregation-induced emission material with a film material, coating the resulting mixture on a glass substrate, and drying to obtain the fluorescent power generation glass.

8. A fluorescent solar concentrator, characterized in that, Comprising the aggregation-induced emission material according to claim 1 or the fluorescent power generation glass according to claim 6.

9. Use of the fluorescent power generation glass according to claim 6 or the fluorescent solar concentrator according to claim 8 in greenhouse cultivation.

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