CN115537196A - High-stability perovskite material and preparation method and application thereof - Google Patents
High-stability perovskite material and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a high-stability perovskite material and a preparation method and application thereof, wherein the preparation method comprises the following steps: firstly, pbBr is added 2 Dissolving in aqueous solution of alkali metal bromide to obtain precursor solution of Pb, and dissolving Cs in aqueous solution of alkali metal bromide 2 CO 3 Dissolving the solution in water to obtain a precursor solution of Cs, and then dropwise adding the precursor solution of Cs into the precursor solution of Pb under the condition of stirring to immediately generate white precipitate. After reacting for a certain time, centrifuging, washing and drying the obtained precipitate to obtain the high-stability perovskite material. The preparation method provided by the invention is simple and easy to implement, the reaction conditions are extremely environment-friendly and mild, the cost is low, macroscopic preparation can be realized, and the obtained high-stability perovskite material has excellent water resistance and high-efficiency photocatalysis property, and has wide application prospects in the fields of photocatalysis, high-efficiency and high-stability LEDs, solar cells and the like.
Description
Technical Field
The invention belongs to the technical field of semiconductor material photocatalysis, and particularly relates to a method for preparing a high-stability perovskite material in a water phase and application of the perovskite material in photocatalytic degradation of dye wastewater.
Background
In recent years, the development of green, environmental-friendly and sustainable chemical engineering is a major challenge facing the current environmental, energy and chemical disciplines. The solar-driven photocatalysis method for degrading environmental pollutants is one of effective ways for solving the current environmental problems, and the perovskite nano material can be used as a novel efficient photocatalysis material due to the advantages of excellent luminescence property, adjustable luminescence wavelength, narrow half-height width of fluorescence peak and the like. Currently, the most widespread chemical synthesis methods for obtaining high quality perovskite nanocrystals are the hot injection method and the room temperature ligand assisted reprecipitation method (LARP). However, for the hot injection method, the experimental process involves the conditions of organic solvent, inert gas, high temperature, vacuum and the like, the conditions are harsh, and the repetition rate is low; the room temperature ligand assisted reprecipitation method has relatively mild reaction conditions, but still inevitably uses a large amount of toxic and harmful polar solvent, and the use of the polar solvent greatly influences the stability of the obtained Nanocrystals (NCs) and causes certain pollution to the environment. Meanwhile, as a novel photocatalyst applied to photocatalytic degradation, the perovskite quantum dot material has the problems of sensitivity to humidity and easy degradation failure in a moisture environment in the photocatalytic degradation application, so that the application of the perovskite quantum dot material in the field is still very limited.
To solve the instability problem of perovskite materials, the current common approaches include: ion doping, surface modification, coating and packaging. For example, patent CN112920792A discloses a method for improving water-oxygen stability of perovskite quantum dot phosphor, which realizes filling of mesopores in the perovskite quantum dot phosphor by selecting recrystallization of appropriate organic metal salt, thereby improving moisture resistance of the perovskite quantum dot phosphor; CN109265664A the invention discloses aThe method for improving the stability of the perovskite material in water by adopting the co-intercalation polymer utilizes the polyethylene glycol-polycaprolactone (PEG-PCL) co-intercalation polymer with amphiphilic property as an embedding material to form a CsPbBr @ PEG-PCL compound, thereby greatly improving the stability of the perovskite compound in an aqueous phase environment; CN108862376A discloses a method for improving stability of fully-inorganic CsPbBr perovskite in aqueous solution, cetyl trimethyl ammonium bromide is used as a cationic surfactant to modify the surface of the perovskite to obtain CsPbBr with good fluorescence stability 3 Solution, prepared CsPbB with stable fluorescence in aqueous solution 3 And (3) solution. CN112408466A discloses a preparation method of a high-stability metal halide perovskite nano composite material, which adopts an in-situ synthesis method to grow CsPbX in situ in a pore structure of an aluminosilicate non-polar polymer 3 Nanocrystals, csPbX is improved 3 Environmental stability of (2). CN113307303A relates to a high-stability all-inorganic perovskite/aluminum phosphate composite nano material, and a preparation method and application thereof. Using AlPO 4 Encapsulated CsPbX 3 The preparation of the ultrahigh stable perovskite nanocrystal is realized. The literature (Xu K, allen A, luo B, vickers E, wang Q, hollingsworth W, ayzner A, li X, zhang J2019J. Phys. Chem. Lett.10 4409) reports that oleic acid, oleylamine and Al (NO: 10) are reprecipitated using a ligand-assisted reprecipitation method 3 ) 3 ·9H 2 Co-modification of CsPbBr by O (ANN) ligand 3 And NCs to obtain the perovskite nano-crystal with good water resistance.
However, the preparation conditions involved in the above methods are complex, and toxic organic solvents or high temperature conditions need to be introduced, which does not meet the environment-friendly preparation requirements; therefore, the method for preparing the perovskite with environmental protection and water resistance is further explored, and the method has important research and application significance.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide a high-stability perovskite material and a preparation method and application thereof. According to the invention, the perovskite with high stability is prepared by adopting a water phase, and the obtained perovskite material has ultrahigh water stability and is expected to be applied to photocatalysis, LED luminescent devices and fluorescent solar collectors; the related preparation method is simple, the reaction condition is mild, no organic solvent is involved, the environment is friendly, and the method is suitable for popularization and application.
The purpose of the invention is realized by the following technical scheme:
a preparation method of a high-stability perovskite material comprises the following steps:
(1) Dissolving alkali metal bromide in water to obtain a solution I; stirring the mixture, adding PbBr 2 Dissolving in the solution I to obtain a solution II;
(2) Mixing Cs 2 CO 3 Dissolving in water to obtain solution III;
(3) Dropwise adding the solution III obtained in the step (2) into the solution II obtained in the step (1) under a stirring state, and reacting;
(4) And (4) centrifuging and washing the mixed solution obtained after the reaction in the step (3) for several times, and drying to obtain the high-stability perovskite material prepared from the water phase.
Preferably, the alkali metal bromide in step (1) is at least one of sodium bromide and potassium bromide.
Preferably, the mass ratio of the alkali metal bromide to the water in the step (1) is 1 (1-2.5).
Preferably, the alkali metal bromide of step (1) and PbBr 2 The mass ratio of (1) is (0.02-0.06).
Preferably, the Cs in step (2) 2 CO 3 The mass ratio of the water to the water is 1 (2-5).
Preferably, the PbBr is prepared in the step (1) 2 And the Cs in the step (2) 2 CO 3 The mass ratio of (1) to (0.5-1).
Preferably, the reaction time in the step (3) is 0-120 min.
Preferably, the washing in step (4) is carried out by water washing.
Preferably, the drying in step (4) is room temperature drying.
The operation or reaction temperature adopted in the steps (1) to (4) of the invention is room temperature.
The high-stability perovskite material prepared by the preparation method of the high-stability perovskite material is provided.
The high-stability perovskite material is applied to photocatalysis, LEDs and fluorescent solar collectors.
Compared with the prior art, the invention has the beneficial effects that:
(1) The invention abandons the organic solvent which is inevitably used in the traditional perovskite material preparation method, excavates a pure water phase perovskite material preparation method, only adopts deionized water as a reaction solvent in the whole experimental process, and skillfully introduces alkali metal bromide to solve PbBr 2 The problem of low solubility in water is solved, the synthesis of perovskite nanocrystals and the in-situ coating of PbBrOH on the surface of the perovskite nanocrystals are synchronously realized, and the stability of the perovskite-based luminescent material is greatly improved;
(2) The method for preparing the high-stability perovskite in the water phase is simple, mild in reaction conditions (only in air environment and room temperature), simple and convenient to operate, capable of realizing macro-preparation, free of introducing toxic ligands or organic solvents, low in preparation cost, environment-friendly and suitable for popularization and application;
(3) The high-stability perovskite prepared by the invention has excellent stability, and has good luminescence performance even if being soaked in water for more than one year, so that the perovskite can be directly used for photocatalytic degradation of organic dyes in water.
Drawings
FIG. 1 is a graph comparing the emission spectrum and the original spectrum of the perovskite product obtained in example 1 after immersion in water for 180 days.
FIG. 2 is a graph comparing the light absorption curves of the high-stability perovskite material prepared in example 1 after photocatalytic degradation and before degradation of dye wastewater.
FIG. 3 is a transmission electron microscope atlas of the high stability perovskite material obtained in example 2.
FIG. 4 is a graph comparing the light absorption curves of the high-stability perovskite material prepared in example 2 after photocatalytic degradation of dye wastewater and before degradation.
FIG. 5 is a diffraction pattern of the high-stability perovskite material obtained in example 3 measured by an X-ray diffractometer.
FIG. 6 is a graph comparing the light absorption curves after photocatalytic degradation and before degradation of the dye wastewater by the high-stability perovskite material prepared in example 3.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
Example 1
A preparation method of a high-stability perovskite material comprises the following steps:
(1) Measuring 4mL of deionized water into a 10mL glass reaction bottle by using a 1mL pipette, weighing 20mmol (2.04 g) of sodium bromide into 4mL of deionized water on an electronic analytical balance, stirring for 5min at the speed of 500rad/min on a magnetic stirrer to fully dissolve the sodium bromide, then continuously weighing 0.27mmol (100 mg) of lead bromide into the sodium bromide concentrated solution, and stirring for 5min at the speed of 500rad/min on the magnetic stirrer to fully dissolve the lead bromide.
(2) 0.2mL of deionized water solution is measured into a 1mL centrifuge tube by using a 1mL pipette, 0.28mmol (90 mg) of cesium carbonate is measured into 0.2mL of deionized water on an electronic analytical balance, and the solution is shaken and shaken for 1min to be dissolved.
(3) Dropwise adding all the solution obtained in the step 2) into the solution obtained in the step 1) on a magnetic stirrer at the speed of 500rad/min, and stopping stirring reaction immediately after dropwise adding.
(4) And (4) centrifuging the solution obtained in the step (3) in a high-speed centrifuge at the speed of 8000rad/min for 5 minutes, removing supernatant after centrifugation, adding deionized water with the same volume for washing and centrifuging, repeating the washing steps twice, and drying at room temperature to obtain the high-stability perovskite powder.
The perovskite product obtained in example 1 was re-soaked in water for 180 days, and the original emission spectrum and the emission spectrum after soaking in water for 180 days (excitation wavelength: 365 nm) were measured, and the results are shown in FIG. 1, and it can be seen from FIG. 1 that: the perovskite material obtained in the embodiment has extremely high water stability in water,the reason why the luminous intensity is not only not reduced but also improved is probably that a small amount of ionic compounds (such as CsBr, cs) are remained on the surface of the material after the material is soaked in water 2 CO 3 ，PbBr 2 Etc.) or surface defects with OH in water - The effect of the method can cause phase generation and agglomeration or electron and hole generation to migrate to the surface of the perovskite to make up for the defects of the surface of the perovskite and the like, so that the fluorescence intensity of the perovskite material is increased after soaking in water, and a foundation is laid for a photocatalysis experiment of the perovskite material in water.
The high-stability perovskite material prepared in the embodiment 1 is used for photocatalytic degradation of dye wastewater, and the specific process is as follows: simulating wastewater organic matters by using methyl orange, adding 1mg of high-stability perovskite material serving as a catalyst into 20mL of methyl orange aqueous solution with the initial concentration of 10mg/L, stirring for 30min under a dark condition to achieve adsorption balance, then placing the methyl orange aqueous solution with the adsorption balance under a xenon lamp (500W, 400nm cut-off short-wave filter) for photocatalysis for 100min, and testing an absorption curve by using an ultraviolet visible near-infrared spectrophotometer; the absorption curve is shown in fig. 2, and it can be seen from fig. 2 that: the catalyst can degrade more than 96% of methyl orange dye within 100min, and the degradation rate is calculated by the following formula: (C) 0 -C/C 0 ) X 100%, where C = highest value of light absorption curve after degradation, C 0 = maximum light absorption curve before degradation.
Example 2
A preparation method of a high-stability perovskite material comprises the following steps:
(1) Taking 4mL of deionized water into a 10mL glass reaction bottle by using a 1mL pipette, weighing 24mmol (2.45 g) of sodium bromide into 4mL of deionized water on an electronic analytical balance, stirring for 5min at the speed of 500rad/min on a magnetic stirrer to fully dissolve the sodium bromide, then continuously weighing 0.27mmol (100 mg) of lead bromide into the concentrated sodium bromide solution, and stirring for 5min at the speed of 500rad/min on the magnetic stirrer to fully dissolve the lead bromide.
(2) 0.2mL of deionized water solution is measured into a 1mL centrifuge tube by using a 1mL pipette, 0.28mmol (90 mg) of cesium carbonate is measured into 0.2mL of deionized water on an electronic analytical balance, and the solution is shaken and shaken for 1min to be dissolved.
(3) And (3) completely dripping the solution obtained in the step (2) into the solution obtained in the step (1) on a magnetic stirrer at the speed of 500rad/min, and continuously stirring for 30min after dripping is finished to fully react.
(4) And (4) centrifuging the solution obtained in the step (3) in a high-speed centrifuge at the speed of 8000rad/min for 5 minutes, removing supernatant after centrifugation, adding deionized water with the same volume for washing and centrifuging, repeating the washing steps twice, and drying at room temperature to obtain the high-stability perovskite powder.
The high-stability perovskite material obtained in example 2 is analyzed by transmission electron microscopy, and the test result is shown in fig. 3, and it can be seen from fig. 3 that: the obtained perovskite material is of a coating structure, which shows that the perovskite material has high stability.
The high-stability perovskite material prepared in example 2 is used for photocatalytic degradation of dye wastewater, the specific process is the same as that of example 1, and the absorption curve is shown in fig. 4, and it can be seen from fig. 4 that: the catalyst can degrade over 99% of methyl orange dye within 100 min.
Example 3
A preparation method of a high-stability perovskite material comprises the following steps:
(1) 4mL of deionized water was weighed into a 10mL glass reaction flask with a 1mL pipette, 36mmol (3.68 g) of sodium bromide was weighed into 4mL of deionized water on an electronic analytical balance, and stirred for 5min at 500rad/min on a magnetic stirrer to dissolve it sufficiently, then 0.27mmol (100 mg) of lead bromide was weighed into the above concentrated sodium bromide solution and stirred for 5min at 500rad/min on a magnetic stirrer to dissolve it sufficiently.
(2) 0.2mL of deionized water solution is measured into a 1mL centrifuge tube by using a 1mL pipette, 0.28mmol (90 mg) of cesium carbonate is measured into 0.2mL of deionized water on an electronic analytical balance, and the solution is shaken and shaken for 1min to be dissolved.
(3) And (3) completely dripping the solution obtained in the step (2) into the solution obtained in the step (1) on a magnetic stirrer at the speed of 500rad/min, and continuously stirring for 120min after dripping is finished so as to fully react.
(4) And (4) centrifuging the solution obtained in the step (3) in a high-speed centrifuge at the speed of 8000rad/min for 5 minutes, removing supernate after centrifugation, adding deionized water with the same volume for washing and centrifuging, repeating the washing steps twice, and drying at room temperature. Finally, the high-stability perovskite powder can be obtained.
The phase analysis of the high-stability perovskite material obtained in example 3 was performed by using an X-ray diffractometer, and the result is shown in fig. 5. As can be seen from fig. 5: the phase composition of the prepared material is PbBrOH @ perovskite.
The phase composition of the desired product of examples 1-2 was the same as in example 3.
The perovskite material with high stability prepared in example 3 can be used for photocatalytic degradation of dye wastewater, the specific process is the same as that of example 1, and the absorption curve is shown in fig. 6, and it can be seen from fig. 6: the catalyst can degrade over 99% of methyl orange dye within 100 min.
The above-described embodiments of the present invention should not be construed as limiting the scope of the present invention. Any other corresponding changes and modifications made according to the technical idea of the present invention should be included in the scope of the claims of the present invention.
Claims (10)
1. A preparation method of a high-stability perovskite material is characterized by comprising the following steps:
(1) Dissolving alkali metal bromide in water to obtain a solution I; stirring the mixture, adding PbBr 2 Dissolving in the solution I to obtain a solution II;
(2) Mixing Cs 2 CO 3 Dissolving in water to obtain solution III;
(3) Dropwise adding the solution III obtained in the step (2) into the solution II obtained in the step (1) under a stirring state, and reacting;
(4) And (4) centrifuging and washing the mixed solution obtained after the reaction in the step (3) for a plurality of times, and drying to obtain the high-stability perovskite material.
2. The method for preparing a high-stability perovskite material according to claim 1, wherein the mass ratio of the alkali metal bromide to the water in the step (1) is 1.
3. The method for preparing the high-stability perovskite material according to claim 2, wherein the alkali metal bromide and PbBr are obtained in the step (1) 2 The mass ratio of (A) to (B) is 1.
4. The process according to any one of claims 1 to 3, wherein the Cs in step (2) is used for preparing the perovskite material with high stability 2 CO 3 And water in a mass ratio of 1.
5. The method for preparing a perovskite material with high stability as claimed in claim 4, wherein the PbBr is prepared in step (1) 2 And (2) the Cs 2 CO 3 The mass ratio of (A) to (B) is 1.
6. The process for preparing a high-stability perovskite material as claimed in any one of claims 1 to 3, wherein the alkali metal bromide in the step (1) is at least one of sodium bromide and potassium bromide.
7. The method for preparing a perovskite material with high stability as claimed in claim 6, wherein the reaction time in the step (3) is 0-120 min.
8. The method for preparing a perovskite material with high stability as claimed in claim 7, wherein the washing in the step (4) is performed by water washing; and (4) drying at room temperature.
9. The high-stability perovskite material prepared by the preparation method of the high-stability perovskite material as claimed in any one of claims 1 to 8.
10. Use of the high stability perovskite material according to claim 9 in photocatalysis, LEDs and fluorescent solar concentrators.
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| CN114525130A (en) * | 2022-02-24 | 2022-05-24 | 华东理工大学 | Metal halide aqueous solution, perovskite fluorescent powder and preparation method thereof |
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| CN114525130A (en) * | 2022-02-24 | 2022-05-24 | 华东理工大学 | Metal halide aqueous solution, perovskite fluorescent powder and preparation method thereof |
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| CN115784301B (en) * | 2023-02-10 | 2023-06-30 | 武汉理工大学 | CsPbBr 3 @TiO 2 Core-shell heterojunction, preparation method and application thereof |
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