CN-122006803-A - Preparation method and application of two-dimensional multilayer D-J halide perovskite

Abstract

The invention discloses a preparation method and application of a two-dimensional multilayer D-J type halide perovskite, wherein aminoethylpyridine is used as an interlayer ligand, formamidine is used as perovskite ions, lead acetate trihydrate is used as a lead source, hydrobromic acid aqueous solution is used as a bromine source and a reaction solvent, the two-dimensional multilayer D-J type halide perovskite is prepared through a one-step solution method, and a target product is obtained through suction filtration, cleaning and drying treatment. Then the target product is dissolved in the mixed organic reagent, and the product with proper size is obtained by using a ligand-assisted anti-solvent method. Different two-dimensional multilayer aromatic DJ halide perovskite can be obtained by selecting the aminoethylpyridine with substituents at different positions. The synthesis method is simple, does not need complex instruments, has short reaction period and is beneficial to large-scale industrial application. The two-dimensional multilayer DJ-type perovskite material prepared by the method can be used for preparing benzaldehyde by efficiently activating toluene C (sp 3 ) -H bonds in a photocatalysis way.

Inventors

• HOU YU
• PENG YU
• WANG XING
• XU YILIN
• YANG HUAGUI

Assignees

• 华东理工大学

Dates

Publication Date

20260512

Application Date

20251226

Claims (10)

1. 1. A method for preparing a two-dimensional multilayer D-J halide perovskite, comprising the steps of: (1) Dissolving lead acetate trihydrate in hydrobromic acid aqueous solution, adding aminoethylpyridine and formamidine acetate to obtain a large amount of bright yellow precipitate, and continuously stirring and heating the mixture until a clear solution is obtained, wherein the molar ratio of the lead acetate trihydrate to the aminoethylpyridine to the formamidine acetate is 100:3.3:36-43; (2) Cooling the clarified solution obtained in the step (1) to room temperature, and obtaining a primary target product through separation, cleaning and drying treatment; (3) And (3) dissolving the primary target product obtained in the step (2) in a polar aprotic solvent containing oleylamine and oleic acid, dripping the formed mixed solution into toluene with intense stirring, centrifuging, washing with toluene for multiple times, and drying to obtain the target product, namely the two-dimensional multilayer D-J type halide perovskite.
2. 2. A method for preparing a two-dimensional multilayer D-J halide perovskite according to claim 1, wherein: wherein in the step (1), the mass fraction of hydrobromic acid in the hydrobromic acid aqueous solution is 48%, and the molar concentration of the lead acetate trihydrate is 2 mmol/mL; the aminoethylpyridine is selected from any one of 3- (2-aminoethyl) pyridine, 2-aminoethylpyridine (2-APD) and 3-aminoethylpyridine (3-APD); The heating temperature of the mixture was 150 ℃.
3. 3. A method of preparing a two-dimensional multilayer D-J halide perovskite according to claim 2, wherein: in the step (2), the drying temperature of the primary target product is 60 ℃.
4. 4. A method for preparing a two-dimensional multilayer D-J halide perovskite according to claim 1, wherein: in the step (3), the polar aprotic solvent is a mixed solution of N, N-dimethylformamide and dimethyl sulfoxide in a volume ratio of 1:1; The volume ratio of oleylamine to the polar aprotic solvent is 1:117, and the volume ratio of oleic acid to the polar aprotic solvent is 1:58.5; the concentration of the primary target product was 66.7 mg/mL.
5. 5. A method for preparing a two-dimensional multilayer D-J halide perovskite according to claim 1, wherein: in the step (3), the volume ratio of the mixed solution to the toluene is 1:100, and the stirring speed of the toluene is 1000 rpm; And (3) after three times of centrifugation and toluene washing, drying at 60 ℃ to obtain the target product, namely the two-dimensional multilayer D-J halide perovskite.
6. 6. A two-dimensional multilayer D-J halide perovskite, characterized in that it is prepared by the preparation method according to any one of claims 1 to 5.
7. 7. The use of the two-dimensional multilayer D-J halide perovskite according to claim 6 for the preparation of a catalyst for photocatalytic oxidation of toluene to benzaldehyde.
8. 8. A catalyst for photocatalytic oxidation of toluene, comprising an active component and an auxiliary material acceptable in the catalyst field, wherein the active component is the two-dimensional multi-layer D-J type halide perovskite according to claim 6.
9. 9. A method for preparing benzaldehyde by photocatalytic oxidation of toluene is characterized by comprising the following steps of taking pure toluene as a reaction liquid, taking the catalyst for photocatalytic oxidation of toluene as a photocatalyst as claimed in claim 8 in a transparent sealed reactor, taking air as a reaction atmosphere, taking a white light LED as a light source, and taking a side irradiation mode as a side irradiation mode.
10. 10. The method for preparing benzaldehyde by photocatalytic oxidation of toluene according to claim 9, wherein: The wavelength of the light source is selected as follows, 420 nm < lambda <780 nm, and the illumination intensity is 150 mW/cm 2 .

Description

Preparation method and application of two-dimensional multilayer D-J halide perovskite Technical Field The invention belongs to the technical field of photocatalysts, relates to a preparation method of a two-dimensional multilayer D-J halide perovskite with photocatalytic activity, and further relates to application of the perovskite as a photocatalyst in photocatalytic oxidation of toluene into benzaldehyde. Background Direct functionalization of the C (sp 3) -H bond to form high value chemicals is one of the most significant challenges in modern chemistry. Among them, the selective oxidation of toluene to benzaldehyde is an important reaction in the production of fine chemicals, fragrances and pharmaceutical intermediates. However, the high bond dissociation energy of the C (sp 3) -H bond in toluene (88.5 kcal/mol) and the poor adsorption properties of toluene make oxidation particularly difficult. Conventional industrial processes, such as thermal oxidation using molecular oxygen under high temperature/pressure conditions, generally require significant energy consumption and high operating costs. Furthermore, these processes exhibit limited product selectivity because benzaldehyde is susceptible to over-oxidation to benzoic acid and even to complete mineralization to carbon dioxide. Photocatalysis is a promising green chemical alternative that can utilize solar energy to oxidize toluene under ambient conditions. This approach avoids the use of harsh thermal/pressure conditions while maintaining sustainability and operational safety. Among the numerous photocatalysts, metal halide perovskite has been attracting attention for its excellent photoelectric properties such as a wide light absorption range, a high light absorption coefficient, and a long carrier diffusion length. In addition, their defect-resistant crystal structure effectively promotes charge transport and suppresses carrier recombination, so that efficient photocatalytic reaction can be achieved. These unique properties make metal halide perovskite an ideal candidate for selective photocatalytic oxidation of toluene to benzaldehyde. Recent researches show that the two-dimensional metal halide perovskite has better environmental stability, and the unique structure of the perovskite endows the perovskite with crystal-dependent asymmetric charge migration prospect, and is expected to realize efficient photocatalytic reaction. Dion-Jacobson (DJ) perovskite layers have no van der Waals gaps between adjacent inorganic layers and are connected by hydrogen bonds, the interlayer forces are stronger, as compared to Ruddlesden-Popper (RP) with a bilayer monoamine organic layer. This structural distinction enhances its stability and promotes charge transport. In addition, as the number of inorganic skeleton layers increases, the exciton binding energy of the quasi-two-dimensional perovskite gradually decreases, and the light absorption range gradually expands, thereby improving the photoelectric performance thereof. Therefore, constructing the two-dimensional multilayer DJ-type perovskite is expected to realize efficient and stable photocatalytic activation of toluene C (sp 3) -H bonds to prepare benzaldehyde. Disclosure of Invention The invention aims at the problems and provides a simple preparation method and photocatalytic application of a novel two-dimensional multilayer DJ perovskite. The preparation method is simple, low in cost and excellent in performance of preparing benzaldehyde by activating toluene C (sp 3) -H bonds through photocatalysis. Complex instruments are not needed in the synthesis process, the operation is convenient, and the method is beneficial to large-scale industrial application. The technical scheme of the invention is summarized as follows, ammonia ethyl pyridine is used as an interlayer ligand, formamidine acetate (FAac) is used as perovskite ion, hydrated lead acetate is used as a lead source, hydrobromic acid aqueous solution is used as a bromine source, a target product is prepared by a simple one-step solution method, and then the target product with the size smaller than 1 mu m is obtained by an antisolvent method by taking oleylamine and oleic acid as ligands. The photocatalyst has excellent performance in the aspect of preparing formaldehyde by photocatalysis of toluene, and has potential application value in other energy development fields. In order to achieve the above purpose, the technical scheme adopted by the invention is as follows: in a first aspect of the present invention, there is provided a method for preparing a two-dimensional multilayered D-J halide perovskite comprising the steps of: (1) Dissolving lead acetate trihydrate in hydrobromic acid aqueous solution, adding aminoethylpyridine and formamidine acetate to obtain a large amount of bright yellow precipitate, and continuously stirring and heating the mixture until a clear solution is obtained, wherein the molar ratio of the lead acetate trihydrate