Doped metal halogenated perovskite photocatalyst as well as preparation method and application thereof

Abstract

The invention belongs to the field of synthesis of sulfoxide compounds, and particularly relates to a doped metal halogenated perovskite photocatalyst as well as a preparation method and application thereof. The preparation method comprises the following steps: adding a DMSO (dimethylsulfoxide) solution containing RuBr3, BiBr3 and CsBr into an isopropanol solution containing citric acid, stirring and reacting to obtain the doped metal halogenated perovskite (Ru-Cs3Bi2Br9), and synthesizing the sulfoxide compound under the conditions of air atmosphere and visible light irradiation by taking the sulphide as a photocatalyst, taking the sulphide as a raw material and taking acetonitrile and water as solvents. By adopting a method of doping Ru < 3 + > with metal halogenated perovskite, efficient catalytic activity and high stability of the metal halogenated perovskite material under oxygen-enriched and high-humidity conditions are realized; the Ru-Cs3Bi2Br9 disclosed by the invention is used as a catalyst, efficient and high-selectivity synthesis of sulfoxide compounds can be realized through visible light irradiation in an air atmosphere at room temperature, and the method is economical, green, high in atom utilization, simple and convenient in post-treatment, low in experimental cost and suitable for large-scale application.

Description

Technical Field

[0001] The invention belongs to the field of sulfoxide compound synthesis, and specifically relates to a doped metal halide perovskite photocatalyst and a preparation method and application thereof. Background Art

[0002] Sulfoxides are important structural units of many fine chemicals such as drug molecules. They play an important role in improving the water solubility of drug molecules, enhancing the ability of drugs to bind to target proteins, and improving the pharmacokinetic process of drug molecules. For example, esomeprazole, as a gastrointestinal drug in clinical practice, is often used to treat gastric ulcers, duodenal ulcers and other related diseases caused by excessive gastric acid secretion. Its secondary metabolites can interact with the proton pump membrane protein on the secretory membrane of gastric parietal cells through disulfide bonds, causing the proton pump membrane protein to be disabled, thereby inhibiting excessive secretion of gastric acid, and then exerting its efficacy in treating diseases related to gastric acid secretion disorders. In addition, sulfoxides, especially chiral sulfoxides, are often used as organic ligands, chiral catalysts, and synthons, etc., and play an important role in the preparation of various chiral catalytic reactions and functional organic molecules. Therefore, the efficient synthesis of sulfoxide compounds has received extensive attention from relevant researchers.

[0003] Sulfide oxidation is one of the most common and effective methods for preparing sulfoxide compounds. In recent years, photocatalysis technology has been widely used as a green and sustainable method to catalyze the oxidation of sulfides and synthesize sulfoxide compounds. However, the catalysts used, such as organic / inorganic semiconductor materials such as organic conjugated polymers, metal organic frameworks, and covalent organic frameworks, generally have the disadvantages of high preparation cost, poor visible light response, fast photogenerated carrier recombination rate, and weak catalytic activity, which are not conducive to the large-scale application of the method. Therefore, the development of a highly selective catalytic system to achieve the green and efficient conversion of sulfides to sulfoxide molecules has become a current research hotspot.

[0004] Metal halide perovskite materials (MHPs) are ideal visible light catalysts due to their sensitive visible light response, long carrier lifetime, easy structural control, and low cost and availability. However, since active oxygen species and water can easily penetrate into the MHPs lattice and cause skeleton degradation, the MHPs are structurally unstable in oxygen-rich and high-humidity environments, which limits their further application research. On the other hand, oxygen and water are natural green reaction reagents. Using them for the synthesis of sulfoxide molecules is not only of great significance for the development of green and sustainable sulfoxide synthesis technology, but also can help 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 highly selectively synthesizing sulfoxide molecules, is an extremely challenging and scientifically meaningful task. Summary of the invention

[0005] The purpose of the present invention is to solve the deficiencies of the prior art. Based on this, the first aspect of the present invention provides a method for preparing a doped metal halide perovskite photocatalyst, comprising the following steps: under stirring conditions, adding a DMSO solution containing RuBr3, BiBr3 and Cs Br to an isopropanol solution containing citric acid, stirring the reaction for 0.5h-2h, centrifuging, discarding the supernatant, washing with isopropanol, and drying to obtain the doped metal halide perovskite, i.e., Ru-Cs3Bi2Br9.

[0006] In some preferred implementations, 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 needs to limit the ratio of the above three raw materials to more accurately meet the above limitations, otherwise it is difficult to ensure that all raw materials react completely. Among them, if the amount of RuBr3 component is too low, the catalytic effect is not good; if it is too high, the catalyst crystal structure is unstable, preferably 0.24 mmol: 0.93 mmol: 1.76 mmol.

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

[0008] In some preferred implementations, the drying conditions include: a drying temperature of 70° C. and a drying time of 6 h to 12 h.

[0009] The second aspect of the present invention provides a doped metal halide perovskite photocatalyst prepared by the above preparation method; and further used in the preparation of sulfoxide compounds by sulfide oxidation method.

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

[0011] Wherein, the sulfoxide compound is an alkyl sulfoxide, an aryl sulfoxide or a heterocyclic sulfoxide, and specifically may be benzyl sulfoxide, dimethyl sulfoxide, 2-pyridazine sulfoxide or sulindac.

[0012] In some preferred implementations, 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 a sulfide in acetonitrile, adding water, irradiating with visible light under an air atmosphere until the reaction is complete, and then centrifuging to recover the catalyst, extracting the obtained 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 the present invention are: the present invention adopts Ru 3+ The method of doping metal halide perovskite realizes the high efficient catalytic activity and high stability of metal halide perovskite materials under oxygen-rich and high humidity conditions; using the Ru-Cs3Bi2Br9 of the present invention as a catalyst, it is possible to realize the high efficient and high selective synthesis of sulfoxide compounds by visible light irradiation in an air atmosphere at room temperature; the method is economical and green, has high atomic utilization, simple post-processing, low experimental cost, and is suitable for large-scale application. BRIEF DESCRIPTION OF THE DRAWINGS

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

[0016] Figure 2 Shown is the NMR hydrogen spectrum of the benzyl sulfoxide product obtained in Example 2;

[0017] Figure 3 Shown is the carbon spectrum of the benzyl sulfoxide product obtained in Example 2;

[0018] Figure 4 Shown is the NMR hydrogen spectrum of the dimethyl sulfoxide product obtained in Example 3;

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

[0020] Figure 6 Shown is the NMR hydrogen spectrum of the 2-pyridazine sulfoxide product obtained in Example 4;

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

[0022] Figure 8 Shown is the NMR hydrogen spectrum of the sulindac product prepared in Example 5;

[0023] Fig. 9 Shown is the carbon spectrum of the sulindac product obtained in Example 5;

[0024] Fig.10 Shown is a global view of the XRD spectra of pure Cs2AgBiBr6 (CABB) and Ru-doped Cs2AgBiBr6 (Ru-CABB);

[0025] Fig.11 This is a partially enlarged view of the XRD spectra of pure Cs2AgBiBr6 (CABB) and Ru-doped Cs2AgBiBr6 (Ru-CABB). DETAILED DESCRIPTION

[0026] The following will be combined with the embodiments and drawings to clearly and completely describe the concept and technical effects of the present invention, so as to fully understand the purpose, scheme and effect of the present invention. It should be noted that the embodiments and features in the embodiments of the present invention can be combined with each other without conflict.

[0027] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as those generally understood by those skilled in the art to which this application belongs. The terms used herein in the specification of this application are only for the purpose of describing specific embodiments and are not intended to limit this application. In this application, unless otherwise specified, the raw materials and equipment used, etc. can be purchased from the market or are commonly used in this field.

[0028] Example 1

[0029] A doped metal halide perovskite photocatalyst, the preparation method of which comprises 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) under rapid stirring and stirred for 1 hour. The resulting yellow solution was centrifuged, the supernatant was discarded, the precipitate was washed 3 times with isopropanol, and dried at 70 ° C for 12 h to obtain Ru 3+ Doped metal halide perovskite (Ru-Cs3Bi2Br9). The obtained material was characterized by XRD, HAADF-STEM, EDS and HRTEM. Figure 1 shown.

[0031] From the XRD pattern ( Figure 1 a) It can be seen that the XRD peak shape does not change significantly before and after the Cs3Bi2Br9 material (CBB) is doped, indicating that Ru doping does not affect the crystal structure of CBB. However, the XRD local enlarged image ( Figure 1b) It can be seen that the diffraction peak of the Ru-doped Cs3Bi2Br9 material (Ru-CBB) shifts slightly to a higher angle, with a shift angle of about 0.15°, indicating that Ru doping causes the lattice contraction of CBB. This result is also verified by high-resolution transmission electron microscopy (HR-TEM). Figure 1 c shows that after Ru doping, the lattice spacing of the CBB material 202 crystal plane is reduced from 0.276nm to 0.274nm. In addition, HAADF-STEM ( Figure 1 d) Analysis shows that Ru-CBB is a regular hexagonal crystal with a smooth surface and a particle size of about 0.2μm. EDS element spectrum analysis ( Figure 1 e) Four elements, Cs, Bi, Br and Ru, were successfully detected, and Ru, like the other three elements, was evenly distributed on the surface of Ru-Cs3Bi2Br9, indicating that Ru was successfully doped into the lattice of Cs3Bi2Br9 instead of gathering on the surface of the material. These results all indicate that the Ru-doped CBB material was successfully prepared.

[0032] Example 2

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

[0034] Weigh thioanisole (1.24 g, 10 mmol) and dissolve it in 6 mL methanol and 0.2 mL distilled water, then add 5 mg Ru-Cs3Bi2Br9, the reaction system is irradiated with visible light in an air atmosphere, and the reaction progress is detected by thin layer chromatography (TLC). After the substrate is completely converted, the photocatalyst is recovered by centrifugation, and the resulting solution is extracted with an organic solvent for 3 times, the organic phases are combined, dried, filtered, and concentrated to obtain a phenyl sulfoxide product (isolation yield: 96%), and the product structure is characterized by NMR analysis technology; its NMR data are shown below, and the hydrogen spectrum and carbon spectrum are shown below Figure 2 and Figure 3 shown.

[0035] Benzyl sulfoxide: colorless oil, 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 comprises the following steps:

[0038] Weigh dimethyl sulfide (0.62 g, 10 mmol) and dissolve it in 6 mL of methanol and 0.2 mL of distilled water, then add 5 mg of Ru-Cs3Bi2Br9, and irradiate the reaction system under visible light in an air atmosphere. Thin layer chromatography (TLC) is used to detect the progress of the reaction. After the substrate is completely converted, the photocatalyst is recovered by centrifugation. The resulting solution is extracted with an organic solvent for three times, and the organic phases are combined, dried, filtered, and concentrated to obtain a dimethyl sulfoxide product (isolation yield: 97%). The product structure is characterized by NMR analysis technology; its NMR data are shown below, and the hydrogen spectrum and carbon spectrum are shown below. Figure 4 and Figure 5 shown.

[0039] Dimethyl sulfoxide: 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 comprises the following steps:

[0042] 2-pyridazine sulfide (1.26 g, 10 mmol) was weighed and dissolved in 6 mL methanol and 0.2 mL distilled water, and then 5 mg Ru-Cs3Bi2Br9 was added. The reaction system was irradiated with visible light in an air atmosphere, and the reaction progress was detected by thin layer chromatography (TLC). After the substrate was completely converted, the photocatalyst was recovered by centrifugation. The resulting solution was extracted with an organic solvent for 3 times, and the organic phases were combined, dried, filtered, and concentrated to obtain a 2-pyridazine sulfoxide product (isolation yield: 92%), and the product structure was characterized by NMR analysis technology; its NMR data are shown below, and the hydrogen spectrum and carbon spectrum are shown as follows: Figure 6 and Figure 7 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 comprises the following steps:

[0046] Sulindac precursor (3.40 g, 10 mmol) was weighed and dissolved in 6 mL methanol and 0.2 mL distilled water, and then 5 mg Ru-Cs3Bi2Br9 was added. The reaction system was irradiated with visible light for 6 hours in an air atmosphere, and the reaction progress was detected by thin layer chromatography (TLC). After the substrate was completely converted, the photocatalyst was recovered by centrifugation. The resulting solution was extracted with an organic solvent for 3 times, and the organic phases were combined, dried, filtered, and concentrated to obtain a sulindac product (isolation yield: 95%), and the product structure was characterized by NMR analysis technology; its NMR data are shown below, and the hydrogen spectrum and carbon spectrum are shown as follows: Figure 8 and Fig. 9 shown.

[0047] Sulindac: 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 comprises 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 (12 mL) solution, and the resulting suspension was transferred to a 25 mL polytetrafluoroethylene reactor and heated at 120 ° C in a muffle furnace for 24 h. The reaction system was then 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 standby use. Fig.10 Shown is the global map of the XRD spectra of pure Cs2AgBiBr6 (CABB) and Ru-doped Cs2AgBiBr6 (Ru-CABB), with the horizontal axis ranging from 5 to 80 degrees, and calculate is the theoretical XED spectrum of CABB; Fig.11 is a local enlarged view with the horizontal axis being 20-50 degrees; Figure 10-11 It can be seen that there is a small angular shift in the diffraction peak after Ru doping. This is because Ru doping causes a change in the lattice of CABB, indicating that the doping is successful.

[0051] A preparation method of 4-methylbenzyl sulfoxide comprises the following steps: weighing 4-methylbenzyl sulfide (1.24 g, 10 mmol) and dissolving it in 6 mL of methanol and 0.2 mL of distilled water, then adding 5 mg of Ru-Cs2AgBiBr6, and irradiating the reaction system under visible light for 2 hours in an air atmosphere; then, centrifuging and recovering the photocatalyst, extracting the reaction system with an organic solvent for 3 times, combining the organic phases, drying, filtering, and concentrating to obtain a benzyl sulfoxide product (isolation yield: 76%).

[0052] The above is only a preferred embodiment of the present invention. The present invention is not limited to the above implementation. As long as the technical effect of the present invention is achieved by the same means, it should belong to the protection scope of the present invention. Within the protection scope of the present invention, its technical scheme and / or implementation method can have various modifications and changes.

Claims

1. A method for preparing a doped metal halide perovskite photocatalyst, characterized in that: The following steps are involved: Under stirring conditions, a DMSO solution containing RuBr3, BiBr3 and CsBr is added to an isopropanol solution containing citric acid, and the reaction is stirred for 0.5h-2h, centrifuged, the supernatant is discarded, 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: 1.76mmol; 0＜x＜1.17。 3. The preparation method according to claim 1, characterized in that: The ratio of RuBr3 and citric acid is (2mmol-4mmol):1mmol.

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

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

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

7. A method for preparing a sulfoxide compound, characterized in that: The following steps are involved: Using sulfide as a raw material, acetonitrile and water as solvents, the doped metal halide perovskite photocatalyst prepared by the preparation method according to any one of claims 1 to 4 or the doped metal halide perovskite photocatalyst according to claim 5 as a catalyst, under the conditions of air atmosphere and visible light irradiation, the sulfoxide compound is prepared.

8. The preparation method according to claim 7, characterized in that: The sulfoxide compound is an alkyl sulfoxide, an aryl sulfoxide or a heterocyclic sulfoxide.

9. The preparation method according to claim 8, characterized in that: The sulfoxide compound is benzyl sulfoxide, dimethyl sulfoxide, 2-pyridazine sulfoxide or sulindac.

10. The preparation method according to claim 7, characterized in that: The preparation method comprises the following steps: dispersing the doped metal halide perovskite photocatalyst prepared by the preparation method according to any one of claims 1 to 4 or the doped metal halide perovskite photocatalyst according to claim 5 as a catalyst and a sulfide in acetonitrile, adding water, irradiating with visible light in an air atmosphere until the reaction is complete, then recovering the catalyst by centrifugation, extracting the obtained solution with an organic solvent, combining the organic phases, drying, filtering and concentrating to obtain the sulfoxide compound.

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