Preparation method for automatically synthesizing perovskite nanorod by using air cannon
Through air cannon technology, the automatic synthesis method of perovskite nanorods is solved, and the problems of difficult to control nucleation and growth rates, difficult to accurately grasp the mixing speed and time, and the use of toxic solvents in the prior art are solved, thus achieving high quality, automated production and safety improvement of perovskite nanorods.
Patent Information
- Application Number
- CN202510011623.7
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-01-04
- Publication Date
- 2025-04-15
AI Technical Summary
The existing chemical synthesis methods of perovskite nanorods have problems such as difficulty in controlling the nucleation and growth rate, difficulty in accurately grasping the mixing rate and time, and the use of toxic organic solvents, resulting in a decrease in crystallization quality and health risks.
Air cannon technology assists the automatic synthesis method of perovskite nanorods, and the rapid mixing and crystallization of anion and cation precursors are promoted through the explosion energy and impact energy of the air cannon, achieving high-quality automated production of perovskite nanorods.
It realizes high-quality and automated production of perovskite nanorods, reduces synthesis costs and health risks, ensures the crystallization quality and fluorescent quantum efficiency of nanorods, and meets the needs of the new generation of high-efficiency lighting and display devices.
Smart Images
Figure CN119822998A_ABST
Abstract
Description
Technical Field
[0001] The invention relates to the technical field of chemical material preparation, and in particular to a preparation method for automatically synthesizing perovskite nanorods by using an air cannon. Background Art
[0002] Perovskite nanorods have attracted widespread attention in the fields of lighting, display, and quantum light sources because their anisotropy of fluorescence distribution is particularly conducive to the extraction of efficient light coupling in semiconductor devices.
[0003] To date, the chemical synthesis of perovskite nanorods has made considerable progress. The commonly used methods for synthesizing perovskite nanorods include high-temperature hot injection, ligand-assisted room temperature supersaturated crystallization, and top-down ultrasonic fragmentation. It is worth noting that the above synthesis methods have gradually exposed the following problems in practice: (1) The nucleation and growth rates are too fast to be accurately controlled, and large-scale preparation is prone to crystallization quality degradation; (2) The mixing speed and mixing time during the synthesis of nanorods are difficult to accurately control, resulting in large quality differences between different batches of perovskite nanorods; (3) The volatilization of toxic organic solvents used in the synthesis process poses a direct threat to the health of the experimenters.
[0004] In order to solve the above-mentioned shortcomings, it is urgently necessary to develop an automated synthesis method for perovskite nanorods, which can not only realize the large-scale automated preparation of perovskite nanorods, reduce the synthesis cost and health risks, but also greatly ensure the crystallization quality of perovskite nanorods. Summary of the invention
[0005] The object of the present invention is to provide a preparation method for automatically synthesizing perovskite nanorods using an air cannon, which is simple and can achieve large-scale automated preparation.
[0006] In order to achieve the above object, the technical solution adopted by the present invention is:
[0007] A method for preparing perovskite nanorods by automatically synthesizing them using an air cannon comprises the following steps:
[0008] (1) dissolving acetate in olefinic acid, and then diluting with a non-polar solvent to obtain a cationic precursor solution; dissolving trimethylhalosilane in fatty amine, and then diluting with a non-polar solvent to obtain an anionic precursor solution;
[0009] (2) Controlling the flow rates of the cationic precursor solution and the anionic precursor solution obtained in step (1) so that the two precursor solutions meet at the air cannon injection port and enter the reaction chamber, and then under the action of the air cannon, the anions and cations are quickly mixed to crystallize into perovskite nanorods.
[0010] The present invention provides an air cannon-assisted perovskite nanorod pipeline flow automatic synthesis method, which uses the blasting energy and impact energy of the air cannon to assist the crystallization of the perovskite nanorods. The most prominent feature is that the blasting energy of the air cannon is used to promote the decomposition of trimethylhalosilane to release halogen anions, and the impact kinetic energy of the air cannon is used to promote the mixing of anions and cations to precipitate perovskite nanorods. The entire synthesis process has a high degree of automation and does not use polar reagents and hazardous chemicals.
[0011] The chemical synthesis method of the perovskite nanorods of the present invention realizes the automated preparation of perovskite nanorods through precursor chemistry and fluid flow, which can ensure the quality of the perovskite nanorods while saving labor costs, and at the same time ensure the biochemical safety of the experimenters. The obtained perovskite nanorods have high fluorescence quantum efficiency, which meets the synthesis requirements of the new generation of high-efficiency lighting and display devices for new semiconductor light-emitting materials.
[0012] Furthermore, the energy of the air cannon in step (2) is 1-9 W / mL, and the action time is 10-90 s.
[0013] Furthermore, in step (2), the flow rate ratio of the cationic precursor solution and the anionic precursor solution when they meet at the injection port is (3-5):1.
[0014] Furthermore, the concentration of the cationic precursor solution in step (1) is 0.05-0.15 mmol / mL.
[0015] Furthermore, the concentration of the anion precursor solution in step (1) is 0.2-0.4 mmol / mL.
[0016] Furthermore, in step (1), the usage ratio of acetate to olefinic acid is 3 mmol:(10-15) mL.
[0017] Furthermore, the acetate is selected from two or more of formamidine acetate, methylamine acetate, cesium acetate, lead acetate, and tin acetate; and the olefinic acid is 10-undecenoic acid or oleic acid.
[0018] Furthermore, in step (1), the molar ratio of trimethylhalosilane to fatty amine is 1:(1-1.5).
[0019] Furthermore, the trimethylhalosilane is trimethylchlorosilane, trimethylbromosilane or trimethyliodosilane; and the fatty amine is n-octylamine or oleylamine.
[0020] Furthermore, the non-polar solvent in step (1) is selected from one or more of n-hexane, cyclohexane, n-octane, n-tridecane and n-nonane.
[0021] The beneficial technical effects of the present invention are:
[0022] (1) The present invention proposes an innovative automatic synthesis method of perovskite nanorods. The method uses air cannon technology and can achieve high-quality, automated production of perovskite nanorods only through basic reactant precursor chemistry and pipeline flow systems. Specifically, during the flow of anion and cation precursor solutions, the mobile impact of the air cannon is used to achieve the mixing of anion and cation precursors to precipitate perovskite nanorods. At the same time, in order to control the crystal growth of anion and cation precursors, trimethylhalosilane is used to carry anions, which can achieve controlled release of halogens and crystal growth of nanorods under the blasting energy of the air cannon. Compared with the existing hot injection method and ligand-assisted high-saturation crystallization method, the preparation method of the present invention does not use dangerous reagents such as toluene in the synthesis process, and can be completed at room temperature, and also supports automated batch synthesis of pipeline flow systems. Compared with the existing ultrasonic crushing method, the preparation method of the present invention is a direct synthesis method. The air cannon can promote the decomposition and mixing of the reaction products, and the crystallization of the obtained product is more controllable.
[0023] (2) The method for preparing perovskite nanorods by automatically synthesizing them using an air cannon has the characteristics of high automation, in-situ detection, and ease of large-scale production. The obtained perovskite nanorods have high fluorescence quantum efficiency (PLQY>95%) and high color purity, which meets the preparation requirements of semiconductor light-emitting materials for the new generation of high-efficiency lighting and display devices.
[0024] (3) The method for preparing perovskite nanorods by automatically synthesizing them using an air cannon is not only low-cost, but also reduces the health hazards of reagents to experimenters during the synthesis process, thereby significantly improving the safety and efficiency of the synthesis process. BRIEF DESCRIPTION OF THE DRAWINGS
[0025] Figure 1 is a schematic diagram of the synthesis of perovskite nanorods according to Example 1 of the present invention;
[0026] Figure 2 is a morphology picture of the perovskite nanorods obtained in Example 1;
[0027] Figure 3 is the fluorescence spectrum of the perovskite nanorods obtained in Example 1;
[0028] Figure 4 is the fluorescence spectrum of the perovskite nanorods obtained in Example 2;
[0029] Figure 5 This is a comparison chart of the fluorescence intensity of perovskite quantum dots under different energies when the air cannon is used. DETAILED DESCRIPTION
[0030] The following is a further detailed description of the present invention in conjunction with specific preferred embodiments, and it cannot be determined that the specific implementation of the present invention is limited to these descriptions. For those of ordinary skill in the technical field to which the present invention belongs, without departing from the concept of the present invention, several simple deductions or replacements can also be made, all of which should be deemed to belong to the protection scope of the present invention. The specific conditions not indicated in the embodiments are carried out according to conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used, unless otherwise specified, are conventional products obtained through commercial channels.
[0031] Example
[0032] Example 1
[0033] This embodiment provides a method for preparing perovskite nanorods by automatically synthesizing them using an air cannon. The method adopts a pipeline flow synthesis technology route, promotes the decomposition of reaction precursors by blasting the air cannon, and uses the impact movement of the air cannon to complete the mixing of anion and cation precursors, thereby crystallizing and precipitating perovskite nanorods. The flow chart of the air cannon-assisted pipeline flow automatic synthesis method of perovskite nanorods is shown in FIG. Figure 1 As shown, it can be implemented by Figure 1 The pipeline flow automation special device shown is mainly composed of two-way microcomputer sample injectors, air cannon reaction chamber and sample collection bottle.
[0034] The specific synthesis method is as follows:
[0035] (1) 1 mmol of lead acetate and 3 mmol of formamidine acetate were dissolved in 10 mL of oleic acid, and then diluted with 30 mL of n-octane to obtain a 0.1 mmol / mL cationic precursor solution; 3 mmol of trimethylsilyl bromide (TMSBr) was dissolved in 3 mmol of oleylamine, and then diluted with 10 mL of n-octane to obtain a 0.3 mmol / mL anionic precursor solution;
[0036] (2) The flow rates of the cationic precursor solution and the anionic precursor solution were controlled so that the two precursor solutions intersected at the injection port at a flow rate ratio of 4:1, and were rapidly mixed for 60 seconds under the action of an air cannon with an energy of 3W / mL. During the mixing process, the explosion of the air cannon promoted the decomposition of trimethylsilyl bromide and released bromide ions. The rapid mixing of anions and cations and the supersaturated crystallization under the action of the ligand precipitated the perovskite nanorods FAPbBr3, which then entered the sample collection bottle.
[0037] Example 2
[0038] The air cannon-assisted pipeline flow automatic synthesis method of perovskite nanorods provided in this embodiment is basically the same as that in Example 1, with the only difference being that in step (1), trimethylsilyl bromide is replaced with trimethylsilyl iodide, and the synthesized sample is FAPbI3 perovskite nanorods.
[0039] Example 3
[0040] This embodiment provides a method for preparing perovskite nanorods by automatically synthesizing them using an air cannon, as follows:
[0041] (1) 0.5 mmol of cesium acetate and 1.5 mmol of methylamine acetate were dissolved in 10 mL of undecylenic acid, and then diluted with 30 mL of n-hexane to obtain a 0.05 mmol / mL cationic precursor solution; 2 mmol of trimethylsilyl iodide was dissolved in 2 mmol of oleylamine, and then diluted with 10 mL of n-hexane to obtain a 0.2 mmol / mL anionic precursor solution;
[0042] (2) The flow rates of the cationic precursor solution and the anionic precursor solution were controlled so that the two precursor solutions intersected at the injection port at a flow rate ratio of 3:1, and were rapidly mixed for 90 seconds under the action of an air cannon with an energy of 1 W / mL. During the mixing process, the explosion of the air cannon promoted the decomposition of trimethyl iodosilane and released iodine ions. The rapid mixing of anions and cations and the supersaturated crystallization under the action of the ligand precipitated the perovskite nanorods FAPbI3, which then entered the sample collection bottle.
[0043] Example 4
[0044] This embodiment provides a method for preparing perovskite nanorods by automatically synthesizing them using an air cannon, as follows:
[0045] (1) 2 mmol of formamidine acetate, 2 mmol of cesium acetate, and 2 mmol of lead acetate were dissolved in 10 mL of oleic acid, and then diluted with a mixture of 15 mL of cyclohexane and 15 mL of n-tridecane to obtain a 0.15 mmol / mL cationic precursor solution; 4 mmol of trimethylsilyl chloride was dissolved in 4 mmol of n-octylamine, and then diluted with a mixture of 5 mL of cyclohexane and 5 mL of n-tridecane to obtain a 0.4 mmol / mL anionic precursor solution;
[0046] (2) The flow rates of the cationic precursor solution and the anionic precursor solution were controlled so that the two precursor solutions intersected at the injection port at a flow rate ratio of 5:1, and were rapidly mixed for 10 seconds under the action of an air cannon with an energy of 9 W / mL. During the mixing process, the explosion of the air cannon promoted the decomposition of trimethylchlorosilane and released chloride ions. The rapid mixing of anions and cations and the supersaturated crystallization under the action of the ligand precipitated the perovskite nanorods FAPbCl3, which then entered the sample collection bottle.
[0047] Embodiment 5-7
[0048] Examples 5-7 are substantially the same as Example 1, except that the energies of the air cannon in step (2) are 2 W / mL, 4 W / mL, and 5 W / mL, respectively.
[0049] Comparative Example
[0050] Comparative Example 1
[0051] Comparative Example 1 is substantially the same as Example 1, except that the energy of the air cannon in step (2) is 0 W / mL and the action time is 0 s, i.e., the air cannon is not used to assist the mixing and crystallization process of the precursor.
[0052] Test example
[0053] Test Example 1
[0054] The morphology of the perovskite nanorods obtained in Example 1 was observed using a transmission electron microscope. Figure 2 .
[0055] Figure 2 is a morphology picture of the perovskite nanorods obtained in Example 1. Figure 2 It can be seen that the perovskite nanorods obtained by the synthesis method provided by the present invention have a nanoscale size of about 10 nm and good size consistency.
[0056] Test Example 2
[0057] The fluorescence spectra of the perovskite nanorods obtained in Example 1 and Example 2 were analyzed using a fluorescence spectrometer. Figure 3 and Figure 4 .
[0058] Figure 3 This is the fluorescence spectrum of the perovskite nanorods obtained in Example 1. Figure 3 It can be seen that the perovskite nanorods obtained in Example 1 have a high fluorescence quantum efficiency, which is close to 100%; the half-peak width of the sample is 19 nm, and the color purity is high. Figure 4 This is a fluorescence spectrum of the perovskite nanorods obtained in Example 2, indicating that the color of the perovskite nanorods prepared by the present invention can be flexibly controlled by changing the halogen composition.
[0059] Test Example 3
[0060] Fluorescence spectrometer was used to investigate the effect of air cannon energy on the fluorescence intensity of perovskite quantum dots. Figure 5 .
[0061] Figure 5 This is a comparison of the fluorescence intensity of perovskite quantum dots under different energies when the air cannon is used. Figure 5 It can be seen that as the energy of the air cannon increases, the fluorescence intensity of the perovskite quantum dots will be significantly enhanced. The above results show that the energy of the air cannon of the present invention can conveniently and effectively achieve the regulation of the fluorescence intensity of the perovskite nanorods, and has strong operability.
[0062] In summary, the present invention proposes an innovative automatic synthesis method for perovskite nanorods, which uses air cannon technology to achieve high-quality, automated production of perovskite nanorods through only basic reactant precursor chemistry and pipeline flow systems. This preparation method is not only low-cost, but also significantly improves the safety and efficiency of the synthesis process, and the resulting perovskite nanorods have high fluorescence quantum efficiency (PLQY>95%) and high color purity, which meets the preparation requirements of semiconductor light-emitting materials for the new generation of high-efficiency lighting and display devices.
[0063] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention, rather than to limit them. The basic principles and main features of the present invention have been described above with specific implementation schemes. On the basis of the present invention, some modifications or replacements may be made thereto, but these modifications or replacements do not make the essence of the corresponding technical solutions deviate from the scope of protection claimed by the present invention.
Claims
1. A method for preparing perovskite nanorods by automatically synthesizing them using an air cannon, characterized in that: The following steps are involved: (1) dissolving acetate in olefinic acid, and then diluting with a non-polar solvent to obtain a cationic precursor solution; dissolving trimethylhalosilane in fatty amine, and then diluting with a non-polar solvent to obtain an anionic precursor solution; (2) Controlling the flow rates of the cationic precursor solution and the anionic precursor solution obtained in step (1) so that the two precursor solutions meet at the air cannon injection port and enter the reaction chamber, and then under the action of the air cannon, the anions and cations are quickly mixed to crystallize into perovskite nanorods.
2. The method for preparing perovskite nanorods automatically synthesized by air cannon as claimed in claim 1, characterized in that: The energy of the air cannon in step (2) is 1-9 W / mL, and the action time is 10-90 s.
3. The method for preparing perovskite nanorods automatically synthesized by air cannon as claimed in claim 1, characterized in that: In step (2), the flow rate ratio of the cationic precursor solution and the anionic precursor solution when they meet at the injection port is (3-5):
1.
4. The method for preparing perovskite nanorods automatically synthesized by air cannon as claimed in claim 3, characterized in that: The concentration of the cationic precursor solution in step (1) is 0.05-0.15 mmol / mL.
5. The method for preparing perovskite nanorods automatically synthesized by air cannon as claimed in claim 3, characterized in that: The concentration of the anion precursor solution in step (1) is 0.2-0.4 mmol / mL.
6. The method for preparing perovskite nanorods automatically synthesized by air cannon as claimed in claim 1, characterized in that: The usage ratio of acetate and olefinic acid in step (1) is 3 mmol: (10-15) mL.
7. The method for preparing perovskite nanorods automatically synthesized by air cannon as claimed in claim 6, characterized in that: The acetate is selected from two or more of formamidine acetate, methylamine acetate, cesium acetate, lead acetate and tin acetate; and the olefinic acid is 10-undecenoic acid or oleic acid.
8. The method for preparing perovskite nanorods automatically synthesized by air cannon as claimed in claim 1, characterized in that: The molar ratio of trimethylhalosilane to fatty amine in step (1) is 1:(1-1.5).
9. The method for preparing perovskite nanorods automatically synthesized by air cannon as claimed in claim 8, characterized in that: The trimethylhalosilane is trimethylchlorosilane, trimethylbromosilane or trimethyliodosilane; the fatty amine is n-octylamine or oleylamine.
10. The method for preparing perovskite nanorods automatically synthesized by air cannon as claimed in claim 1, characterized in that: The non-polar solvent in step (1) is selected from one or more of n-hexane, cyclohexane, n-octane, n-tridecane and n-nonane.