A doped metal halide perovskite photocatalyst, and a preparation method and application thereof

Abstract

This invention belongs to the field of sulfoxide compound synthesis, specifically relating to a doped metal halide perovskite photocatalyst, its preparation method, and its application. The doped metal halide perovskite (Ru-Cs3Bi2Br9) is obtained by adding a DMSO solution containing RuBr3, BiBr3, and CsBr to an isopropanol solution containing citric acid and stirring. Then, using this as a photocatalyst, with sulfides as raw materials and acetonitrile and water as solvents, sulfoxide compounds are synthesized under air atmosphere and visible light irradiation. This invention uses Ru... 3+ The method of doping metal halide perovskites achieves high efficiency and high stability of metal halide perovskite materials under oxygen-rich and high-humidity conditions. Using Ru-Cs3Bi2Br9 of this invention as a catalyst, sulfoxide compounds can be synthesized efficiently and selectively by visible light irradiation in air at room temperature. The method is economical and green, with high atom utilization, simple post-processing, and low experimental cost, making it suitable for large-scale application.

Description

Technical Field

[0001] This invention belongs to the field of sulfoxide compound synthesis, specifically relating to a doped metal halide perovskite photocatalyst, its preparation method, and its application. Background Technology

[0002] Sulfoxides are important structural units in many fine chemicals, including pharmaceutical molecules, playing a crucial role in improving the water solubility of drug molecules, enhancing the binding affinity between drugs and target proteins, and improving the pharmacokinetic processes of drug molecules. For example, esomeprazole, a gastrointestinal drug commonly used clinically to treat diseases caused by excessive gastric acid secretion, such as gastric ulcers and duodenal ulcers, has secondary metabolites that interact with proton pump membrane proteins on the secretory membrane of gastric parietal cells via disulfide bonds, causing the proton pump membrane proteins to become inactive and thus inhibiting excessive gastric acid secretion, thereby exerting its therapeutic effect on diseases related to gastric acid secretion disorders. In addition, sulfoxides, especially chiral sulfoxides, are also frequently used as organic ligands, chiral catalysts, and synthons, playing an important role in various chiral catalytic reactions and the preparation of functional organic molecules. Therefore, the efficient synthesis of sulfoxide compounds has attracted widespread attention from researchers.

[0003] Thioether oxidation is one of the most common and efficient methods for preparing sulfoxides. In recent years, photocatalysis, as a green and sustainable method, has been widely used to catalyze the oxidation of thioethers to synthesize sulfoxides. However, the catalysts used, such as organic conjugated polymers, metal-organic frameworks, and covalent organic frameworks (organic / inorganic semiconductor materials), generally suffer from drawbacks such as high preparation costs, poor visible light response, fast photogenerated carrier recombination rates, and weak catalytic activity, which are not conducive to the large-scale application of the method. Therefore, developing highly selective catalytic systems to achieve the green and efficient conversion of thioethers to sulfoxide molecules has become a current research hotspot.

[0004] Metal halide perovskite (MHPs) materials possess advantages such as high visible light response, long carrier lifetime, easily tunable structure, and low cost and availability, making them ideal visible light photocatalysts. However, the infiltration of reactive oxygen species and water into the MHP lattice, leading to framework degradation, makes MHPs structurally unstable under oxygen-rich and high-humidity environments, limiting their further application research. On the other hand, oxygen and water are natural and green reaction reagents; using them for the synthesis of sulfoxide molecules is not only significant for developing green and sustainable sulfoxide synthesis technologies but also contributes to the low-carbon and green development of the chemical industry. Therefore, achieving high structural stability and high catalytic activity of MHPs under oxygen-rich and high-humidity conditions, while simultaneously synthesizing sulfoxide molecules with high selectivity, is a highly challenging and scientifically significant endeavor. Summary of the Invention

[0005] The purpose of this invention is to overcome the shortcomings of the prior art. Based on this, the first aspect of this invention provides a method for preparing a doped metal halide perovskite photocatalyst, comprising the following steps: under stirring conditions, a DMSO solution containing RuBr3, BiBr3 and CsBr is added to an isopropanol solution containing citric acid, the mixture is stirred and reacted for 0.5 h to 2 h, centrifuged, the supernatant is discarded, the mixture is washed with isopropanol, and dried to obtain the doped metal halide perovskite, namely Ru-Cs3Bi2Br9.

[0006] In some preferred embodiments, the ratio of RuBr3, BiBr3, and CsBr is x mmol : (1.17-x) mmol : 1.76 mmol; 0 < x < 1.17. The above preparation method requires that the ratio of the three raw materials be precisely controlled to meet the above limitations; otherwise, it is difficult to ensure that all raw materials react completely. Specifically, if the amount of RuBr3 is too low, the catalytic effect is poor; if it is too high, the catalyst crystal structure is unstable. The preferred ratio is 0.24 mmol : 0.93 mmol : 1.76 mmol.

[0007] In some preferred embodiments, the ratio of RuBr3 to citric acid is (2mmol-4mmol):1mmol. If the amount of citric acid is too low, it will affect the crystallization state of the catalyst; if the amount is too high, it will increase the cost and waste resources; the preferred ratio is 1.76mmol:0.52mmol.

[0008] In some preferred embodiments, the drying conditions include a drying temperature of 70°C and a drying time of 6-12 hours.

[0009] A second aspect of the present invention provides a doped metal halide perovskite photocatalyst prepared by the above-described preparation method; and further applies it to the preparation of sulfoxide compounds by the sulfide oxidation method.

[0010] Based on the above-mentioned doped metal halide perovskite photocatalysts and their applications, a third aspect of the present invention provides a method for preparing sulfoxide compounds, comprising the following steps: using sulfides as raw materials, acetonitrile and water as solvents, and the above-mentioned doped metal halide perovskite photocatalyst as a catalyst, the sulfoxide compounds are prepared under air atmosphere and visible light irradiation conditions.

[0011] The sulfoxide compound is an alkyl sulfoxide, aryl sulfoxide, or heterocyclic sulfoxide. Specifically, it can be benzyl sulfoxide, dimethyl sulfoxide, 2-pyridazine sulfoxide, or sulinic acid.

[0012] In some preferred embodiments, the preparation method of the above-mentioned sulfoxide compounds includes the following steps: dispersing the above-mentioned doped metal halide perovskite photocatalyst as a catalyst and sulfide in acetonitrile, adding water, irradiating with visible light in an air atmosphere until the reaction is complete, then centrifuging to recover the catalyst, extracting the resulting solution with an organic solvent, combining the organic phases, drying, filtering, and concentrating to obtain the sulfoxide compounds.

[0013] The drying process can be carried out using anhydrous sodium sulfate.

[0014] The beneficial effects of this invention are as follows: This invention uses Ru 3+ The method of doping metal halide perovskites achieves high catalytic activity and high stability of metal halide perovskite materials under oxygen-rich and high-humidity conditions. Using Ru-Cs3Bi2Br9 of this invention as a catalyst, sulfoxide compounds can be synthesized efficiently and selectively by visible light irradiation in air at room temperature. The method is economical and green, with high atom utilization, simple post-processing, and low experimental cost, making it suitable for large-scale application. Attached Figure Description

[0015] Figure 1 The XRD, HRTEM, HAADF-STEM spectra and EDS elemental energy spectrum analysis of Ru-Cs3Bi2Br9 prepared in Example 1 are shown.

[0016] Figure 2 The image shows the NMR spectrum of the benzene sulfoxide product obtained in Example 2;

[0017] Figure 3 The image shown is the carbon spectrum of the benzene sulfoxide product obtained in Example 2;

[0018] Figure 4 The image shows the NMR spectrum of the dimethyl sulfoxide product obtained in Example 3.

[0019] Figure 5 The image shown is the carbon spectrum of the dimethyl sulfoxide product obtained in Example 3;

[0020] Figure 6 The image shows the 1H NMR spectrum of the 2-pyridazine sulfoxide product obtained in Example 4.

[0021] Figure 7 The image shown is the carbon spectrum of the 2-pyridazine sulfoxide product obtained in Example 4;

[0022] Figure 8 The image shows the 1H NMR spectrum of the sulindac product obtained in Example 5;

[0023] Figure 9 The image shown is the carbon spectrum of the sulindac product obtained in Example 5;

[0024] Figure 10 The image shows a global view of the XRD patterns of pure Cs2AgBiBr6 (CABB) and Ru-doped Cs2AgBiBr6 (Ru-CABB);

[0025] Figure 11 This is a magnified view of the XRD patterns of pure Cs2AgBiBr6 (CABB) and Ru-doped Cs2AgBiBr6 (Ru-CABB). Detailed Implementation

[0026] The following will provide a clear and complete description of the concept and technical effects of the present invention in conjunction with the embodiments and accompanying drawings, so as to fully understand the purpose, solution and effects of the present invention. It should be noted that, unless otherwise specified, the embodiments and features in the embodiments of the present invention can be combined with each other.

[0027] Unless otherwise defined, 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 application belongs. The terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the application. Unless otherwise specified, the materials and equipment used in this application are commercially available or commonly used in the art.

[0028] Example 1

[0029] A doped metal halide perovskite photocatalyst, the preparation method of which includes the following steps:

[0030] CsBr (0.3745 g, 1.76 mmol), BiBr3 (0.4199 g, 0.93 mmol), and RuBr3 (0.08 g, 0.24 mmol) were dissolved in DMSO (10 mL). The resulting solution was added to isopropanol (120 mL) containing citric acid (0.1 g, 0.52 mmol) with rapid stirring, and stirred for 1 hour. The resulting yellow solution was centrifuged, the supernatant was discarded, and the precipitate was washed three times with isopropanol and dried at 70 °C for 12 h to obtain RuBr3. 3+ Doped metal halide perovskite (Ru-Cs3Bi2Br9). The obtained material was characterized structurally using XRD, HAADF-STEM, EDS, and HRTEM techniques. The results are shown below. Figure 1 As shown.

[0031] From the XRD pattern ( Figure 1 a) It can be seen that the peak shape of the XRD pattern did not change significantly before and after doping of Cs3Bi2Br9 material (CBB), indicating that Ru doping does not affect the crystal structure of CBB. However, through the magnified XRD pattern ( Figure 1(b) It can be seen that the diffraction peaks of the Ru-doped Cs3Bi2Br9 material (Ru-CBB) are slightly shifted to higher angles, with a shift angle of approximately 0.15°. This indicates that Ru doping causes lattice shrinkage in CBB, a result that was also verified by high-resolution transmission electron microscopy (HR-TEM). Figure 1 As can be seen from c, after Ru doping, the lattice spacing of the 202 crystal plane of the CBB material decreased from 0.276 nm to 0.274 nm. Furthermore, HAADF-STEM ( Figure 1 d) Analysis shows that Ru-CBB is a regular hexagonal crystal with a smooth surface and a particle size of approximately 0.2 μm. EDS elemental energy dispersive spectroscopy analysis (…) Figure 1 e) Four elements, Cs, Bi, Br, and Ru, were successfully detected. Furthermore, Ru, like the other three elements, was uniformly distributed on the Ru-Cs3Bi2Br9 surface, indicating that Ru was successfully doped into the Cs3Bi2Br9 lattice rather than agglomerated on the material surface. These results demonstrate the successful preparation of Ru-doped CBB materials.

[0032] Example 2

[0033] A method for preparing a sulfoxide compound includes the following steps:

[0034] Anisole (1.24 g, 10 mmol) was dissolved in 6 mL of methanol and 0.2 mL of distilled water, and then 5 mg of Ru-Cs3Bi2Br9 was added. The reaction system was irradiated under visible light in an air atmosphere. The reaction progress was monitored by thin-layer chromatography (TLC). After complete substrate conversion, the photocatalyst was recovered by centrifugation. The resulting solution was extracted three times with an organic solvent. The organic phases were combined, dried, filtered, and concentrated to obtain the anisole sulfoxide product (separation yield: 96%). The structure of the product was characterized by NMR analysis. The NMR data are shown below, and the proton and carbon spectra are as follows. Figure 2 and Figure 3 As shown.

[0035] Benzyl sulfoxide: a colorless oily substance. 1 H NMR (500MHz, CDCl3) δ (ppm) 7.64 (ddt, J = 7.1, 3.7, 1.6Hz, 2H), 7.53 (dt, J = 6.4, 2.0Hz, 1H), 7.52–7.44 (m, 2H), 2.71 (dd, J = 4.2, 1.6Hz, 3H); 13 C{H}NMR (126MHz, CDCl3) δ (ppm) 145.65, 131.07, 129.39, 123.51, 43.97.

[0036] Example 3

[0037] A method for preparing a sulfoxide compound includes the following steps:

[0038] Dimethyl sulfide (0.62 g, 10 mmol) was dissolved in 6 mL of methanol and 0.2 mL of distilled water, and then 5 mg of Ru-Cs3Bi2Br9 was added. The reaction system was irradiated under visible light in an air atmosphere. The reaction progress was monitored by thin-layer chromatography (TLC). After complete substrate conversion, the photocatalyst was recovered by centrifugation. The resulting solution was extracted three times with an organic solvent. The organic phases were combined, dried, filtered, and concentrated to obtain the dimethyl sulfoxide product (separation yield: 97%). The structure of the product was characterized by NMR analysis. The NMR data are shown below, and the proton and carbon spectra are as follows. Figure 4 and Figure 5 As shown.

[0039] Dimethyl sulfoxide: a colorless liquid. 1 H NMR (500MHz, CDCl3) δ (ppm) 2.55 (d, J = 1.4Hz, 3H).; 13 C{H}NMR (126MHz, CDCl3) δ (ppm) 40.99ppm.

[0040] Example 4

[0041] A method for preparing a sulfoxide compound includes the following steps:

[0042] 1.26 g (10 mmol) of 2-pyridazine sulfide was dissolved in 6 mL of methanol and 0.2 mL of distilled water. 5 mg of Ru-Cs3Bi2Br9 was then added. The reaction system was irradiated under visible light in an air atmosphere. The reaction progress was monitored by thin-layer chromatography (TLC). After complete substrate conversion, the photocatalyst was recovered by centrifugation. The resulting solution was extracted three times with an organic solvent. The organic phases were combined, dried, filtered, and concentrated to obtain the 2-pyridazine sulfoxide product (separation yield: 92%). The product structure was characterized by NMR analysis. The NMR data are shown below, and the proton and carbon spectra are as follows: Figure 6 and Figure 7 As shown.

[0043] 2-Pyridazine sulfoxide: Yellow liquid. 1 H NMR (500MHz, CDCl3) δ (ppm) 8.87 (t, J = 4.0Hz, 2H), 7.41 (d, J = 4.7Hz, 1H), 2.93 (d, J = 4.2Hz, 3H).; 13 C{H}NMR (126MHz, CDCl3) δ (ppm) 174.18, 158.55, 121.78, 40.28.

[0044] Example 5

[0045] A method for preparing sulindac includes the following steps:

[0046] Sulindac precursor (3.40 g, 10 mmol) was dissolved in 6 mL of methanol and 0.2 mL of distilled water, followed by the addition of 5 mg of Ru-Cs3Bi2Br9. The reaction system was irradiated under visible light in air for 6 hours. The reaction progress was monitored by thin-layer chromatography (TLC). After complete substrate conversion, the photocatalyst was recovered by centrifugation. The resulting solution was extracted three times with an organic solvent. The organic phases were combined, dried, filtered, and concentrated to obtain the sulindac product (separation yield: 95%). The product structure was characterized by NMR analysis. The NMR data are shown below, and the proton and carbon spectra are as follows. Figure 8 and Figure 9 As shown.

[0047] Sulinic acid: a yellow solid. 1 H NMR(500MHz, CDCl3)δ(ppm)7.73–7.68(m,2H),7.64(d,J=8.1Hz,2H),7.14(s,1H),7.11(dd,J=8.3,5.1H z,1H),6.88(dd,J=8.8,2.4Hz,1H),6.54(td,J=8.8,2.4Hz,1H),3.58(s,2H),2.83(s,3H),2.20(s,3H).; 13 C{H}NMR(126MHz,CDCl3)δ(ppm)174.66,164.33,162.37,146.59,146.52,144.88,141.64,139.80,138.44,131.44,131 .42,130.28,129.44,129.42,128.31,128.29,123.97,123.74,123.67,110.96,110.78,106.25,106.06,43.60,31.41.

[0048] Comparative Example 1

[0049] The preparation method of Ru-Cs2AgBiBr6 includes the following steps:

[0050] CsBr (0.424 g, 2.0 mmol), BiBr3 (0.358 g, 0.8 mmol), RuBr3 (0.067 g, 0.2 mmol), and AgBr (0.19 g, 1.0 mmol) were dispersed in a 48% HBr solution (12 mL). The resulting suspension was transferred to a 25 mL polytetrafluoroethylene reactor and heated in a muffle furnace at 120 °C for 24 h. Subsequently, the reaction system was cooled to room temperature at a cooling rate of 1 °C / h, the solid was separated by centrifugation, and washed several times with isopropanol to obtain Ru-doped Cs2AgBiBr6 material, which was then dried at 120 °C for 2 h for later use. Figure 10 The image shows a global view of the XRD spectra of pure Cs2AgBiBr6 (CABB) and Ru-doped Cs2AgBiBr6 (Ru-CABB), with the horizontal axis representing 5-80 degrees. The calculated value is the theoretical XRD spectrum of CABB. Figure 11 This is a magnified view of a section with an x-axis of 20-50 degrees; from Figures 10-11 It can be seen that the diffraction peaks exhibit a small angular shift after Ru doping. This is due to the lattice change in CABB caused by Ru doping, indicating that the doping was successful.

[0051] A method for preparing 4-methylbenzyl sulfoxide includes the following steps: 1.24 g (10 mmol) of 4-methylbenzyl sulfide is weighed and dissolved in 6 mL of methanol and 0.2 mL of distilled water, and then 5 mg of Ru-Cs2AgBiBr6 is added. The reaction system is irradiated under visible light in an air atmosphere for 2 hours. Subsequently, the photocatalyst is recovered by centrifugation, and the resulting solution is extracted three times with an organic solvent. The organic phases are combined, dried, filtered, and concentrated to obtain the benzyl sulfoxide product (separation yield: 76%).

[0052] The above description is merely a preferred embodiment of the present invention. The present invention is not limited to the above-described embodiments. Any embodiment that achieves the technical effects of the present invention using the same means should fall within the protection scope of the present invention. Within the protection scope of the present invention, various modifications and variations can be made to the technical solutions and / or implementation methods.

Claims

1. A method for preparing a doped metal halide perovskite photocatalyst, characterized in that, Includes the following steps: Under stirring conditions, a DMSO solution containing RuBr3, BiBr3 and CsBr was added to an isopropanol solution containing citric acid. The mixture was stirred for 0.5 h to 2 h, centrifuged, the supernatant was discarded, and the mixture was washed with isopropanol and dried to obtain the doped metal halide perovskite, namely Ru-Cs3Bi2Br9.

2. The preparation method according to claim 1, characterized in that, The ratio of RuBr3, BiBr3 and CsBr is x mmol: (1.17-x) mmol: 1.76 mmol; 0 < x < 1.

17.

3. The preparation method according to claim 1, characterized in that, The ratio of RuBr3 to citric acid is (2 mmol-4 mmol): 1 mmol.

4. The preparation method according to claim 1, characterized in that, The drying conditions include a drying temperature of 70 ℃ and a drying time of 6 h to 12 h.

5. A doped metal halide perovskite photocatalyst, characterized in that, It is prepared by the preparation method according to any one of claims 1 to 4.

6. The application of the doped metal halide perovskite photocatalyst according to claim 5 in the preparation of sulfoxide compounds by sulfide oxidation.

7. A method for preparing a sulfoxide compound, characterized in that, Includes the following steps: Using sulfides as raw materials, acetonitrile and water as solvents, and the doped metal halide perovskite photocatalyst of claim 5 as a catalyst, the sulfoxide compound is prepared under air atmosphere and visible light irradiation conditions.

8. The preparation method according to claim 7, characterized in that, The sulfoxide compounds are alkyl sulfoxides, aryl sulfoxides, or heterocyclic sulfoxides.

9. The preparation method according to claim 7, characterized in that, The sulfoxide compounds are benzyl sulfoxide, dimethyl sulfoxide, 2-pyridazine sulfoxide, or sulinic acid.

10. The preparation method according to claim 7, characterized in that, The preparation method includes the following steps: dispersing the doped metal halide perovskite photocatalyst of claim 5 as a catalyst and sulfide in acetonitrile, adding water, irradiating with visible light in an air atmosphere until the reaction is complete, then centrifuging to recover the catalyst, extracting the resulting solution with an organic solvent, combining the organic phases, drying, filtering, and concentrating to obtain the sulfoxide compound.

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