Carbon-nitrogen group modified inverse opal bismuth-based halide perovskite material, preparation method and application method

Abstract

This invention relates to a carbon-nitrogen group-modified inverse opal bismuth halide perovskite material, its preparation method, and its application. The preparation method includes: mixing a carbon-nitrogen precursor with the inverse opal bismuth halide perovskite material, followed by calcination to obtain the carbon-nitrogen group-modified inverse opal bismuth halide perovskite material. This invention significantly enhances the application of the inverse opal bismuth halide perovskite material in the photocatalytic oxidative coupling reaction of benzylamine by modifying its surface with carbon-nitrogen groups. It exhibits excellent catalytic activity and selectivity under long-wavelength light irradiation. Furthermore, the preparation method provided by this invention is simple and reproducible, offering a new technical solution for the application of bismuth halide perovskite materials in organic oxidation reactions.

Description

Technical Field

[0001] This invention relates to the field of catalysis technology, specifically to inorganic functional materials, and more particularly to a carbon-nitrogen group-modified inverse opal bismuth-based haloperovskite material, its preparation method, and its application method. Background Technology

[0002] Imine compounds are widely present in people's production and daily life. Due to their unique biological activities, they are often used to synthesize antibacterial and antitumor drugs. The electrophilic C=N region provides a favorable coordination environment for imine compounds, making them readily coordinate with transition metals to form organometallic complexes, which can be used to prepare multifunctional materials. Simultaneously, the active C=N region and the designable active metal centers (especially transition and noble metals) in imines make them valuable in catalysis and organic synthesis. The synthesis of imines is mainly achieved through the condensation reaction of aldehydes or ketones with amines under acid catalysis. This process usually requires the participation of active aldehydes and dehydrating agents, and demanding reaction conditions such as high temperature and high pressure.

[0003] From a sustainable development perspective, solar energy is a renewable and clean energy source that is not limited by time or location. Efficiently converting solar energy into chemical energy is one of the most promising strategies for solving the energy crisis and environmental problems. In the photocatalytic oxidative coupling of benzylamine, inexpensive and clean molecular oxygen is used as the oxidant, and the reaction proceeds under relatively mild conditions. This high-efficiency, low-pollution synthesis strategy provides a novel approach for preparing high-value-added imines.

[0004] CN120381859A discloses the application of a SiC quantum dot (SiC) catalyst in the photocatalytic oxidative coupling reaction of benzylamine. The catalyst uses SiC as a raw material. The specific preparation process is as follows: SiC is dispersed in a mixed aqueous solution of hydrofluoric acid and nitric acid, heated to 100°C in a hydrothermal reactor and maintained for 1-6 hours. After removal and cooling to room temperature, it is diluted with deionized water and ultrasonically vibrated. Then, the acid is removed by centrifugation to obtain neutral large particles, which are then dispersed in deionized water, ultrasonically vibrated, centrifuged again, and the supernatant is collected and freeze-dried to obtain the SiC quantum dot (SiC QDs) catalyst. Using the above-mentioned SiC QDs catalyst, efficient photocatalytic oxidative coupling of benzylamine can be achieved in an air atmosphere.

[0005] CN111470539A discloses a method for preparing a highly efficient catalyst for the oxidative coupling of benzylamine. Ultrathin tungsten disulfide nanosheets with surface texture were synthesized via an oil-phase method. The preparation process is simple, reproducible, and exhibits novel morphology. The synthesized tungsten disulfide demonstrates excellent catalytic activity for the oxidative coupling of benzylamine to imine. At 60°C, without the need for additional light source or oxygen, and under indoor illumination in an air atmosphere, using acetonitrile as a solvent, a yield of up to 97.91%, a conversion rate of 98.61%, and a selectivity of 99.29% can be achieved after 30 hours of reaction. Furthermore, this catalytic reaction exhibits excellent cycle stability.

[0006] CN113546647A discloses a method for preparing and applying a defective ultrathin nanosheet self-assembled nanosphere. In this invention, the defective ultrathin nanosheet self-assembled nanosphere is composed of a single layer of BiOBr nanosheets with a diameter of 0.9~1.3 μm and an average thickness of 3.0 nm for the ultrathin BiOBr nanosheets that make up the nanosphere. The defective ultrathin nanosheet self-assembled nanosphere prepared by this invention exhibits high activity in the catalytic oxidation of benzylamine to imine under visible light in an air atmosphere.

[0007] Therefore, it is of great significance to provide a highly efficient photocatalytic catalyst for the oxidative coupling of benzylamine to benzylenebenzylamine. Summary of the Invention

[0008] To address the shortcomings of existing technologies, the present invention aims to provide a carbon-nitrogen group-modified inverse opal bismuth halide perovskite material, its preparation method, and its application method. This invention significantly enhances the application of inverse opal bismuth halide perovskite materials in the photocatalytic oxidative coupling reaction of benzylamine by modifying the surface of the material with carbon-nitrogen groups. It exhibits excellent catalytic activity and selectivity under long-wavelength light irradiation. Furthermore, the preparation method provided by this invention is simple and reproducible, offering a new technical solution for the application of bismuth halide perovskite materials in organic oxidation reactions.

[0009] To achieve this objective, the present invention adopts the following technical solution: In a first aspect, the present invention provides a method for preparing a carbon-nitrogen group-modified inverse opal bismuth-based halide perovskite material, the preparation method comprising: A carbon-nitrogen precursor was mixed with an inverse opal bismuth-based haloperovskite material, and then calcined to obtain the carbon-nitrogen group-modified inverse opal bismuth-based haloperovskite material. Among various narrow bandgap semiconductor materials, bismuth-based halide perovskite materials are not only inexpensive, thermally stable, and less toxic, but also possess good resistance to moisture. Compared to conventional bulk bismuth-based halide perovskite materials, inverse opal bismuth-based halide perovskite materials consist of regularly arranged channels with thin and continuous pore walls, which significantly increases the specific surface area of ​​the material. This facilitates the exposure of more surface active sites, enhances the contact efficiency between reactants and catalysts, and its regular pore wall structure provides a stable support for surface modification, enabling precise control of surface electronic structure and interface properties.

[0010] This invention modifies the surface of anti-opal bismuth-based haloperovskite materials with carbon and nitrogen groups, effectively regulating the electronic structure of the material surface, increasing the number of active sites, and significantly improving its application in the photocatalytic oxidative coupling reaction of benzylamine. The photoresponse range is extended to 700 nm, and it also exhibits excellent catalytic activity and selectivity under long-wavelength light irradiation. Furthermore, the preparation method provided by this invention is simple and reproducible, offering a new technical solution for the application of bismuth-based haloperovskite materials in organic oxidation reactions.

[0011] Preferably, the carbon-nitrogen precursor includes any one or a combination of at least two of ammonium carbamate, ammonium formate, urea, ammonium citrate, ammonium acetate, ammonium propionate, ammonium oxalate, or ammonium tartrate.

[0012] Preferably, the inverse opal bismuth-based haloperovskite material includes any one or a combination of at least two of inverse opal Cs3Bi2Br9, inverse opal Cs3Bi2Cl9, or inverse opal Cs3Bi2I9.

[0013] Preferably, the average pore size of the inverse opal bismuth-based haloperovskite material is 50 nm to 800 nm.

[0014] Preferably, the mass ratio of the carbon-nitrogen precursor to the inverse opal bismuth-based haloperovskite material is (0.05~200):1.

[0015] Preferably, the roasting temperature is 300℃~800℃.

[0016] Preferably, the roasting time is 1 hour to 10 hours.

[0017] Preferably, the heating rate of the calcination is 1℃ / min to 10℃ / min.

[0018] Preferably, the roasting atmosphere includes any one of air, argon, or nitrogen.

[0019] In a second aspect, the present invention provides a carbon-nitrogen group-modified inverse opal bismuth-based haloperovskite material, wherein the carbon-nitrogen group-modified inverse opal bismuth-based haloperovskite material is prepared by the preparation method described in the first aspect; the carbon-nitrogen group-modified inverse opal bismuth-based haloperovskite material comprises an inverse opal bismuth-based haloperovskite matrix and carbon-nitrogen groups modified on the surface of the bismuth-based haloperovskite matrix.

[0020] Thirdly, the present invention provides a method for applying carbon-nitrogen group-modified anti-opite bismuth-based halide perovskite materials in the photocatalytic oxidative coupling reaction of benzylamine, the method comprising: The carbon-nitrogen group-modified inverse opal bismuth-based haloperovskite material as described in the first aspect is dispersed with benzylamine in a solvent, and the light source is turned on to initiate the photocatalytic oxidative coupling reaction of benzylamine.

[0021] Preferably, the amount of the carbon-nitrogen group-modified inverse opal bismuth-based haloperovskite material added is 3 mg / mL to 5 mg / mL.

[0022] Preferably, the amount of benzylamine added is 0.01 mmol / mL to 0.05 mmol / mL.

[0023] Preferably, the solvent includes any one of ethyl acetate, acetonitrile, methanol, ethanol, or 1,4-dioxane.

[0024] Preferably, the photocatalytic oxidative coupling reaction of benzylamine is carried out under stirring at a stirring rate of 100 rpm to 1000 rpm.

[0025] Preferably, the photocatalytic oxidative coupling reaction of benzylamine takes place over a period of 0.1 h to 48 h.

[0026] Preferably, the light source includes an LED light source with a wavelength of 360nm to 800nm ​​or a xenon lamp.

[0027] Compared with the prior art, the present invention has the following beneficial effects: This invention modifies the surface of anti-opal bismuth-based haloperovskite materials with carbon and nitrogen groups, effectively controlling the electronic structure of the material surface, increasing the number of active sites, and extending the photoresponse range to 700 nm. This significantly improves its application in the photocatalytic oxidative coupling reaction of benzylamine, exhibiting excellent catalytic activity and selectivity under long-wavelength light irradiation. Furthermore, the preparation method provided by this invention is simple and reproducible, offering a new technical solution for the application of bismuth-based haloperovskite materials in organic oxidation reactions. Attached Figure Description

[0028] Figure 1 This is a SEM image of the carbon-nitrogen group-modified inverse opal Cs3Bi2Br9 prepared in Example 1.

[0029] Figure 2 This is an XRD comparison image of inverse opal Cs3Bi2Br9 before and after surface modification with carbon and nitrogen groups, as provided in Preparation Example 1.

[0030] Figure 3 The images show the UV-Vis spectra of inverse opal Cs3Bi2Br9 before and after surface modification with carbonitriding groups, as provided in Preparation Example 1.

[0031] Figure 4 The images show the infrared spectra of inverse opal Cs3Bi2Br9 before and after surface modification with carbon and nitrogen groups, as provided in Preparation Example 1.

[0032] Figure 5 The graph shows the photocatalytic benzylamine oxidation performance of the inverse opal Cs3Bi2Br9 with surface-modified carbon and nitrogen groups provided in Example 1 under different wavelength light sources.

[0033] Figure 6 This is a SEM image of the carbon-nitrogen group-modified inverse opal Cs3Bi2Cl9 prepared in Example 2.

[0034] Figure 7 This is a SEM image of the carbon-nitrogen group-modified inverse opal Cs3Bi2I9 prepared in Example 3.

[0035] Figure 8 This is a SEM image of the carbon-nitrogen group-modified inverse opal Cs3Bi2Br9 prepared in Example 4.

[0036] Figure 9 This is a SEM image of the carbon-nitrogen group-modified inverse opal Cs3Bi2Br9 prepared in Example 5. Detailed Implementation

[0037] The technical solution of the present invention will be further illustrated below through specific embodiments. Those skilled in the art should understand that the preparation examples are merely illustrative of the present invention and should not be considered as specific limitations thereof.

[0038] The "range" disclosed in this invention can be defined in the form of a lower limit and an upper limit. A given range is defined by selecting a lower limit and an upper limit, which define the boundaries of the specific range. This type of range definition can include or exclude endpoints; any endpoint can be independently included or excluded, and they can be arbitrarily combined, meaning any lower limit can be combined with any upper limit to form a range. For example, if ranges of 60~120 and 80~110 are listed for specific parameters, it is understood that ranges of 60~110 and 80~120 are also expected. Furthermore, if minimum range values ​​1 and 2 are listed, and maximum range values ​​3, 4, and 5 are also listed, then the following ranges are all expected: 1~3, 1~4, 1~5, 2~3, 2~4, and 2~5. In this invention, unless otherwise stated, the numerical range "a~b" represents a shortened representation of any combination of real numbers between a and b, where a and b are real numbers. For example, the numerical range "0~5" indicates that all real numbers between "0" and "5" have been listed in this article; "0~5" is simply a shortened representation of these numerical combinations. Furthermore, when a parameter is described as an integer ≥2, it is equivalent to listing integers such as 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, etc. For instance, when a parameter is described as an integer selected from "2~10", it is equivalent to listing the integers 2, 3, 4, 5, 6, 7, 8, 9, and 10.

[0039] In this invention, "a combination of at least two" refers to a quantity greater than or equal to two, unless otherwise specified. For example, "any combination of one or at least two" means one or more or more items. It can be understood that when referring to "a combination of at least two," it refers to any suitable combination of multiple items, that is, a combination of "at least two" items carried out in a manner that does not conflict with and enables the implementation of this invention.

[0040] Unless otherwise specified, all embodiments and optional embodiments of the present invention can be combined with each other to form new technical solutions.

[0041] The term "preparation example" as used in this invention means that a specific feature, structure, or property described in connection with a preparation example may be included in at least one preparation example or embodiment of the invention. The appearance of this phrase in various places in the specification does not necessarily refer to the same preparation example, nor is it an independent or alternative preparation example mutually exclusive with other preparation examples. It will be explicitly and implicitly understood by those skilled in the art that the preparation examples described in this invention can be combined with other preparation examples.

[0042] Those skilled in the art will understand that the order in which the steps are written in the methods of each preparation example does not imply a strict execution order. The detailed execution order of each step should be determined by its function and possible internal logic. Unless otherwise specified, all steps of the present invention may be performed sequentially or randomly, but are preferably performed sequentially. For example, the method includes steps (a) and (b), indicating that the method may include steps (a) and (b) performed sequentially, or it may include steps (b) and (a) performed sequentially. For example, the method may also include step (c), indicating that step (c) may be added to the method in any order. For example, the method may include steps (a), (b), and (c), or it may include steps (a), (c), and (b), or it may include steps (c), (a), and (b), etc.

[0043] In this invention, open-ended technical features or solutions described using terms such as "comprising" do not exclude additional members beyond those listed unless otherwise specified. They can be considered as providing both closed-ended features or solutions comprised of the listed members and open-ended features or solutions that include additional members beyond the listed members. For example, A includes a1, a2, and a3. Unless otherwise specified, it may also include other members or exclude additional members. This can be considered as providing both technical features or solutions where "A is composed of a1, a2, and a3" or "A is selected from a1, a2, and a3," and technical features or solutions where "A includes not only a1, a2, and a3, but also other members."

[0044] In this invention, unless otherwise specified, the features or solutions corresponding to "and / or" include any one of two or more of the related listed items, as well as any and all combinations of the related listed items. These arbitrary and all combinations include any two related listed items, any more related listed items, or a combination of all related listed items. For example, "A and / or B" represents a group consisting of A, B, and "a combination of A and B". "Containing A and / or B" can mean "containing A, containing B, and containing A and B", or "containing A, containing B, or containing A and B", and can be appropriately understood according to the context.

[0045] In this invention, the terms "first aspect," "second aspect," "third aspect," etc., are used for descriptive purposes only and should not be construed as indicating or implying relative importance or quantity, nor should they be construed as implicitly indicating the importance or quantity of the indicated technical features. Moreover, "first," "second," "third," etc., serve only as a non-exhaustive enumeration and should be understood not to constitute a closed limitation on the quantity.

[0046] In this invention, "optional" means that something is optional, that is, it refers to either "with" or "without". If there are multiple "optional" options in a technical solution, unless otherwise specified, and there are no contradictions or mutual constraints, then each "optional" option is independent.

[0047] In this invention, unless otherwise specified, the processes are assumed to be carried out at room temperature or at temperatures conventionally set in the art. "Room temperature" generally refers to 4°C to 35°C, and may refer to 20°C ± 5°C. In some preparation examples of this invention, room temperature refers to 20°C to 30°C.

[0048] In one specific embodiment, the present invention provides a method for preparing a carbon-nitrogen group-modified anti-opal bismuth-based halide perovskite material, the preparation method comprising: A carbon-nitrogen precursor is mixed with an inverse opal bismuth-based haloperovskite material and calcined to obtain the carbon-nitrogen group-modified inverse opal bismuth-based haloperovskite material.

[0049] Among various narrow bandgap semiconductor materials, bismuth-based halide perovskite materials are not only inexpensive, thermally stable, and less toxic, but also possess good resistance to moisture. Compared to conventional bulk bismuth-based halide perovskite materials, inverse opal bismuth-based halide perovskite materials consist of regularly arranged channels with thin and continuous pore walls, which significantly increases the specific surface area of ​​the material. This facilitates the exposure of more surface active sites, enhances the contact efficiency between reactants and catalysts, and its regular pore wall structure provides a stable support for surface modification, enabling precise control of surface electronic structure and interface properties.

[0050] This invention involves calcining a carbon-nitrogen-modified inverse opal bismuth halide perovskite material with a carbon-nitrogen precursor. The carbon-nitrogen precursor undergoes thermal decomposition, forming a carbon-nitrogen group layer containing C–N bonds on the surface of the carbon-nitrogen-modified inverse opal bismuth halide perovskite material. By modifying the surface of the inverse opal bismuth halide perovskite material with carbon-nitrogen groups, this invention effectively regulates the electronic structure of the material surface, increases the number of active sites, and significantly improves its application in the photocatalytic oxidative coupling reaction of benzylamine, extending the photoresponse range to 700 nm. It also exhibits excellent catalytic activity and selectivity under long-wavelength illumination. Furthermore, the preparation method provided by this invention is simple and reproducible, offering a new technical solution for the application of bismuth halide perovskite materials in organic oxidation reactions.

[0051] In some embodiments, the carbon-nitrogen precursor includes any one or a combination of at least two of ammonium carbamate, ammonium formate, urea, ammonium citrate, ammonium acetate, ammonium propionate, ammonium oxalate, or ammonium tartrate.

[0052] In some embodiments, the inverse opal bismuth-based haloperovskite material includes any one or a combination of at least two of inverse opal Cs3Bi2Br9, inverse opal Cs3Bi2Cl9, or inverse opal Cs3Bi2I9.

[0053] In some embodiments, the average pore size of the inverse opal bismuth-based haloperovskite material is 50 nm to 800 nm, for example, it can be 50 nm, 100 nm, 200 nm, 300 nm, 400 nm, 500 nm, 600 nm, 700 nm or 800 nm.

[0054] In some embodiments, the mass ratio of the carbon-nitrogen precursor to the inverse opal bismuth-based haloperovskite material is (0.05~200):1, for example, it can be 0.05:1, 0.1:1, 0.2:1, 0.5:1, 1:1, 5:1, 10:1, 20:1, 30:1, 40:1, 50:1, 100:1, 150:1 or 200:1, etc.

[0055] In some embodiments, the calcination temperature is 300℃~800℃, for example, it can be 300℃, 350℃, 400℃, 450℃, 500℃, 550℃, 600℃, 650℃, 700℃, 750℃ or 800℃, etc.

[0056] In some embodiments, the roasting time is 1h to 10h, for example, it can be 1h, 2h, 3h, 4h, 5h, 6h, 7h, 8h, 9h or 10h.

[0057] In some embodiments, the heating rate of the calcination is 1℃ / min to 10℃ / min, for example, it can be 1℃ / min, 2℃ / min, 3℃ / min, 4℃ / min, 5℃ / min, 6℃ / min, 7℃ / min, 8℃ / min, 9℃ / min or 10℃ / min, etc.

[0058] In some embodiments, the roasting atmosphere includes any one of air, argon, or nitrogen.

[0059] In some embodiments, when the calcination atmosphere includes argon or nitrogen, the argon or nitrogen introduction rate is 20 mL / min to 100 mL / min, for example, it can be 20 mL / min, 30 mL / min, 40 mL / min, 50 mL / min, 60 mL / min, 70 mL / min, 80 mL / min, 90 mL / min or 100 mL / min, etc.

[0060] In another specific embodiment, the present invention provides a carbon-nitrogen group-modified inverse opal bismuth halide perovskite material, wherein the carbon-nitrogen group-modified inverse opal bismuth halide perovskite material is prepared by the preparation method described in one of the preceding specific embodiments; the carbon-nitrogen group-modified inverse opal bismuth halide perovskite material comprises an inverse opal bismuth halide perovskite matrix and carbon-nitrogen groups modified on the surface of the bismuth halide perovskite matrix.

[0061] In yet another specific embodiment, the present invention provides a method for applying carbon-nitrogen group-modified anti-opite bismuth-based halide perovskite materials in the photocatalytic oxidative coupling reaction of benzylamine, the method comprising: The carbon-nitrogen group-modified inverse opal bismuth-based haloperovskite material, as described in one of the aforementioned specific embodiments, is dispersed in a solvent with benzylamine. The light source is turned on to initiate the photocatalytic oxidative coupling reaction of benzylamine.

[0062] In some embodiments, the amount of the carbon-nitrogen group-modified inverse opal bismuth halide perovskite material added is 3 mg / mL to 5 mg / mL, for example, it can be 3 mg / mL, 3.5 mg / mL, 4 mg / mL, 4.5 mg / mL or 5 mg / mL, etc.

[0063] In some embodiments, the amount of benzylamine added is 0.01 mmol / mL to 0.05 mmol / mL, for example, it can be 0.01 mmol / mL, 0.02 mmol / mL, 0.03 mmol / mL, 0.04 mmol / mL or 0.05 mmol / mL, etc.

[0064] In some embodiments, the solvent includes any one of ethyl acetate, acetonitrile, methanol, ethanol, or 1,4-dioxane.

[0065] In some embodiments, the photocatalytic oxidative coupling reaction of benzylamine is carried out under stirring at a speed of 100 rpm to 1000 rpm, such as 100 rpm, 200 rpm, 300 rpm, 400 rpm, 500 rpm, 600 rpm, 700 rpm, 800 rpm, 900 rpm, or 1000 rpm.

[0066] In this invention, the photocatalytic oxidative coupling reaction of benzylamine is carried out at room temperature. Room temperature in this invention refers to a temperature of 20°C to 30°C, such as 20°C, 22°C, 24°C, 25°C, 26°C, 28°C, or 30°C.

[0067] In some embodiments, the photocatalytic oxidative coupling reaction of benzylamine takes place over a period of 0.1 h to 48 h, for example, 0.1 h, 1 h, 2 h, 4 h, 6 h, 12 h, 16 h, 18 h, 24 h, 30 h, 36 h, or 48 h.

[0068] In some embodiments, the light source includes an LED light source or a xenon lamp with a wavelength of 360nm to 800nm. The wavelength of the light source may be, for example, 360nm, 400nm, 410nm, 450nm, 500nm, 530nm, 550nm, 600nm, 650nm, 700nm, 750nm, or 800nm.

[0069] The numerical range described in this invention includes not only the point values ​​listed above, but also any point values ​​within the numerical ranges not listed above. Due to space limitations and for the sake of brevity, this invention will not exhaustively list all the specific point values ​​included in the range.

[0070] Preparation Example 1 This preparation example provides a method for preparing a carbon-nitrogen group-modified inverse opal bismuth-based halide perovskite material, the preparation method comprising: Ammonium carbamate and inverse opal Cs3Bi2Br9 with an average pore size of 360 nm were mixed at a mass ratio of 10:1. The mixture was placed in a muffle furnace and calcined at 300 °C at a rate of 5 °C / min for 2 h in air atmosphere to obtain the carbon-nitrogen group-modified inverse opal Cs3Bi2Br9.

[0071] In this preparation example, the SEM image of the carbon-nitrogen group-modified inverse opal Cs3Bi2Br9 is shown below. Figure 1 As shown, the XRD patterns of inverse opal Cs3Bi2Br9 before and after surface modification with carbon and nitrogen groups are as follows. Figure 2 As shown, the crystal structure of inverse opal Cs3Bi2Br9 remains unchanged before and after modification; the UV-Vis spectra of inverse opal Cs3Bi2Br9 before and after surface modification with carbon and nitrogen groups are as follows. Figure 3 As shown, after surface modification with carbon-nitrogen groups, the photoresponse range expanded from 480 nm to 700 nm. The infrared spectra of inverse opal Cs3Bi2Br9 before and after surface modification with carbon-nitrogen groups are shown below. Figure 4 As shown, carbon-nitrogen group-modified inverse opal Cs3Bi2Br9 at 2225 cm⁻¹ -1 and 2050cm -1 The presence of distinct characteristic peaks at these locations corresponds to ν(C≡N) (cyano stretching vibration) and ν(N≡C), respectively, demonstrating that carbon and nitrogen groups were successfully modified onto the Cs3Bi2Br9 surface.

[0072] Preparation Example 2 This preparation example provides a method for preparing a carbon-nitrogen group-modified inverse opal bismuth-based haloperovskite material. The preparation method is the same as in Preparation Example 1, except that the inverse opal Cs3Bi2Br9 with an average pore size of 360 nm is replaced with inverse opal Cs3Bi2Cl9 with an average pore size of 120 nm.

[0073] In this preparation example, the SEM image of inverse opal Cs3Bi2Cl9 is as follows: Figure 6 As shown.

[0074] Preparation Example 3 This preparation example provides a method for preparing a carbon-nitrogen group-modified inverse opal bismuth-based halide perovskite material. The preparation method is the same as in Preparation Example 1, except that the inverse opal Cs3Bi2Br9 with an average pore size of 360 nm is replaced with inverse opal Cs3Bi2I9 with an average pore size of 240 nm.

[0075] In this preparation example, the SEM images of inverse opal Cs3Bi2I9 are as follows: Figure 7 As shown.

[0076] Preparation Example 4 This preparation example provides a method for preparing a carbon-nitrogen group-modified inverse opal bismuth-based halide perovskite material. The preparation method is the same as in Preparation Example 1, except that the inverse opal Cs3Bi2Br9 with an average pore size of 360 nm is replaced with inverse opal Cs3Bi2Br9 with an average pore size of 480 nm.

[0077] In this preparation example, the SEM images of inverse opal Cs3Bi2Br9 are as follows: Figure 8 As shown.

[0078] Preparation Example 5 This preparation example provides a method for preparing a carbon-nitrogen group-modified inverse opal bismuth-based halide perovskite material. The preparation method is the same as in Preparation Example 1, except that the inverse opal Cs3Bi2Br9 with an average pore size of 360 nm is replaced with inverse opal Cs3Bi2Br9 with an average pore size of 600 nm.

[0079] In this preparation example, the SEM images of inverse opal Cs3Bi2Br9 are as follows: Figure 9 As shown.

[0080] Preparation Example 6 This preparation example provides a method for preparing a carbon-nitrogen group-modified inverse opal bismuth-based haloperovskite material. Except for replacing ammonium carbamate with an equal mass of ammonium formate in the preparation method, the rest is the same as in Preparation Example 1.

[0081] Preparation Example 7 This preparation example provides a method for preparing a carbon-nitrogen group-modified inverse opal bismuth-based halide perovskite material, the preparation method comprising: Ammonium citrate and inverse opal Cs3Bi2Br9 with an average pore size of 360 nm were mixed at a mass ratio of 5:1. The mixture was placed in a muffle furnace and calcined at 450 °C for 4 h under air atmosphere at a rate of 3 °C / min to obtain the carbon-nitrogen group-modified inverse opal Cs3Bi2Br9.

[0082] Preparation Example 8 This preparation example provides a method for preparing a carbon-nitrogen group-modified inverse opal bismuth-based haloperovskite material. Except for replacing ammonium carbamate with urea and using a mass ratio of urea to inverse opal Cs3Bi2Br9 of 4:1, the preparation method is the same as in Preparation Example 1.

[0083] Preparation Example 9 This preparation example provides a method for preparing a carbon-nitrogen group-modified inverse opal bismuth-based haloperovskite material. Except for adjusting the mass ratio of ammonium carbamate to inverse opal Cs3Bi2Br9 to 1:1, the preparation method is the same as in Preparation Example 1.

[0084] Preparation Example 10 This preparation example provides a method for preparing a carbon-nitrogen group-modified inverse opal bismuth-based haloperovskite material. Except for adjusting the mass ratio of ammonium carbamate to inverse opal Cs3Bi2Br9 to 50:1, the preparation method is the same as in Preparation Example 1.

[0085] Preparation Example 11 This preparation example provides a method for preparing a carbon-nitrogen group-modified inverse opal bismuth-based halide perovskite material, the preparation method comprising: Ammonium carbamate and inverse opal Cs3Bi2Br9 with an average pore size of 800 nm were mixed at a mass ratio of 150:1. The mixture was placed in a muffle furnace and calcined at 350 °C at a rate of 10 °C / min for 1 h in air atmosphere to obtain the carbon-nitrogen group-modified inverse opal Cs3Bi2Br9.

[0086] Preparation Example 12 This preparation example provides a method for preparing a carbon-nitrogen group-modified inverse opal bismuth-based halide perovskite material, the preparation method comprising: Ammonium carbamate and inverse opal Cs3Bi2Br9 with an average pore size of 50 nm were mixed at a mass ratio of 0.1:1. The mixture was placed in a muffle furnace, nitrogen gas was introduced at a rate of 50 mL / min, the temperature was increased to 300 °C at a rate of 1 °C / min, and calcined for 10 h to obtain the carbon-nitrogen group modified inverse opal Cs3Bi2Br9.

[0087] Comparative Preparation Example 1 This comparative preparation example provides a method for preparing a carbon-nitrogen group-modified inverse opal bismuth-based haloperovskite material. The preparation method is the same as that in Preparation Example 1, except that non-inverse opal blocky Cs3Bi2Br9 is used to replace the inverse opal Cs3Bi2Br9 in Preparation Example 1 with an equal mass.

[0088] Application Example 1 This application example provides a method for using the carbon-nitrogen group-modified anti-opal Cs3Bi2Br9 prepared in Example 1 in the photocatalytic oxidative coupling reaction of benzylamine, the application method comprising: At room temperature, carbon-nitrogen group-modified inverse opal Cs3Bi2Br9 was used as a catalyst and dispersed with benzylamine in ethyl acetate. The amount of carbon-nitrogen group-modified inverse opal Cs3Bi2Br9 added was 4 mg / mL, and the amount of benzylamine added was 0.02 mmol / mL. The resulting mixture was placed in a stainless steel reactor with a quartz lens, and the reactor was purged with air 5 times. The reaction was carried out under LED light with a wavelength of 530 nm and stirred at 500 rpm for 12 h. After the reaction was completed, the supernatant was obtained by centrifugation and used for gas chromatography analysis.

[0089] Application Example 2 This application example provides a method for using the carbon-nitrogen group-modified anti-opal Cs3Bi2Cl9 prepared in Preparation Example 2 in the photocatalytic oxidative coupling reaction of benzylamine, and the application method is the same as that in Application Example 1.

[0090] Application Example 3 This application example provides a method for using the carbon-nitrogen group-modified anti-opal Cs3Bi2I9 prepared in Preparation Example 3 in the photocatalytic oxidative coupling reaction of benzylamine, and the application method is the same as that in Application Example 1.

[0091] Application Example 4 This application example provides a method for using the carbon-nitrogen group-modified anti-opal Cs3Bi2Br9 prepared in Preparation Example 4 in the photocatalytic oxidative coupling reaction of benzylamine, and the application method is the same as that in Application Example 1.

[0092] Application Example 5 This application example provides a method for using the carbon-nitrogen group-modified anti-opal Cs3Bi2Br9 prepared in Preparation Example 5 in the photocatalytic oxidative coupling reaction of benzylamine, and the application method is the same as that in Application Example 1.

[0093] Application Example 6 This application example provides a method for using the carbon-nitrogen group-modified anti-opal Cs3Bi2Br9 prepared in Preparation Example 6 in the photocatalytic oxidative coupling reaction of benzylamine. The application method is the same as that in Application Example 1, except that the reaction time is adjusted from 12h to 16h.

[0094] Application Example 7 This application example provides a method for using the carbon-nitrogen group-modified anti-opal Cs3Bi2Br9 prepared in Preparation Example 7 in the photocatalytic oxidative coupling reaction of benzylamine, and the application method is the same as that in Application Example 1.

[0095] Application Example 8 This application example provides a method for using the carbon-nitrogen group-modified anti-opal Cs3Bi2Br9 prepared in Preparation Example 8 in the photocatalytic oxidative coupling reaction of benzylamine. The application method is the same as that in Application Example 1, except that the reaction time is adjusted from 12h to 30h.

[0096] Application Example 9 This application example provides a method for using the carbon-nitrogen group-modified anti-opal Cs3Bi2Br9 prepared in Preparation Example 9 in the photocatalytic oxidative coupling reaction of benzylamine, and the application method is the same as that in Application Example 1.

[0097] Application Example 10 This application example provides a method for using the carbon-nitrogen group-modified anti-opal Cs3Bi2Br9 prepared in Preparation Example 10 in the photocatalytic oxidative coupling reaction of benzylamine, and the application method is the same as that in Application Example 1.

[0098] Application Example 11 This application example provides a method for using the carbon-nitrogen group-modified anti-opal Cs3Bi2Br9 prepared in Example 1 in the photocatalytic oxidative coupling reaction of benzylamine. The application method is the same as that in Application Example 1, except that the reaction is stirred for 5 hours under LED light irradiation at a wavelength of 450 nm.

[0099] Application Example 12 This application example provides a method for using the carbon-nitrogen group-modified anti-opal Cs3Bi2Br9 prepared in Example 1 in the photocatalytic oxidative coupling reaction of benzylamine. The application method is the same as in Application Example 1, except that the solvent is replaced by an equal volume of 1,4-dioxane instead of ethyl acetate.

[0100] Application Example 13 This application example provides a method for applying the carbon-nitrogen group-modified anti-opal Cs3Bi2Br9 prepared in Example 1 in the photocatalytic oxidative coupling reaction of benzylamine. The application method is the same as in Application Example 1, except that the solvent is replaced by an equal volume of acetonitrile instead of ethyl acetate, and the reaction is stirred for 4 hours under LED light irradiation at a wavelength of 410 nm.

[0101] Application Example 14 This application example provides a method for applying the carbon-nitrogen group-modified anti-opal Cs3Bi2Br9 prepared in Example 1 in the photocatalytic oxidative coupling reaction of benzylamine. The application method is the same as in Application Example 1, except that the solvent is replaced by an equal volume of methanol instead of ethyl acetate and the reaction time is adjusted from 12 h to 24 h.

[0102] Application Example 15 This application example provides a method for using the carbon-nitrogen group-modified anti-opal Cs3Bi2Br9 prepared in Preparation Example 11 in the photocatalytic oxidative coupling reaction of benzylamine, the application method comprising: At room temperature, carbon-nitrogen group-modified inverse opal Cs3Bi2Br9 was used as a catalyst and dispersed with benzylamine in ethyl acetate. The amount of carbon-nitrogen group-modified inverse opal Cs3Bi2Br9 added was 3 mg / mL, and the amount of benzylamine added was 0.01 mmol / mL. The resulting mixture was placed in a stainless steel reactor with a quartz lens, and the reactor was purged with air 5 times. The reaction was carried out under LED light with a wavelength of 360 nm and stirred at 100 rpm for 48 h. After the reaction was completed, the supernatant was obtained by centrifugation and used for gas chromatography analysis.

[0103] Application Example 16 This application example provides a method for using the carbon-nitrogen group-modified anti-opal Cs3Bi2Br9 prepared in Preparation Example 12 in the photocatalytic oxidative coupling reaction of benzylamine, the application method comprising: At room temperature, carbon-nitrogen group-modified inverse opal Cs3Bi2Br9 was used as a catalyst and dispersed with benzylamine in ethyl acetate. The amount of carbon-nitrogen group-modified inverse opal Cs3Bi2Br9 added was 5 mg / mL, and the amount of benzylamine added was 0.05 mmol / mL. The resulting mixture was placed in a stainless steel reactor with a quartz lens, and the reactor was purged with air 5 times. The reaction was carried out under an LED lamp with a wavelength of 800 nm and stirred at 900 rpm for 0.5 h. After the reaction was completed, the supernatant was obtained by centrifugation and used for gas chromatography analysis.

[0104] Comparative Application Example 1 This comparative application example provides a method for directly applying the anti-opal Cs3Bi2Br9 provided in Preparation Example 1, without modification of carbon and nitrogen groups, to the photocatalytic oxidative coupling reaction of benzylamine. The application method is the same as that in Application Example 1, except that the anti-opal Cs3Bi2Br9 provided in Preparation Example 1 is used directly as the catalyst.

[0105] Comparative Application Example 2 This comparative application example provides a method for using non-inverse opal-structured bulk Cs3Bi2Br9 in the photocatalytic oxidative coupling reaction of benzylamine. The method is the same as that in Application Example 1, except that non-inverse opal-structured bulk Cs3Bi2Br9 is used as the catalyst.

[0106] Comparative Application Example 3 This comparative application example provides a method for applying the carbon-nitrogen group-modified bulk Cs3Bi2Br9 prepared in Comparative Preparation Example 1 in the photocatalytic oxidative coupling reaction of benzylamine. The application method is the same as that in Application Example 1, except that the carbon-nitrogen group-modified bulk Cs3Bi2Br9 provided in this comparative application example is used as the catalyst.

[0107] Performance testing: Gas chromatography was used to analyze the components of the supernatant obtained by centrifugation in all the above application examples and comparative application examples. The conversion rate of benzylamine and the selectivity of imine were tested. The test results are shown in Table 1.

[0108] This invention also tested the application of the surface-modified carbon-nitrogen group-modified inverse opal Cs3Bi2Br9 provided in Example 1 to the photocatalytic oxidative coupling reaction of benzylamine. Under otherwise unchanged conditions, the wavelength affected the conversion rate of benzylamine and the selectivity for imines. The test results are shown in […]. Figure 5 The material provided by this invention also exhibits excellent catalytic activity and selectivity under long-wavelength light irradiation.

[0109] Table 1 In summary, this invention significantly enhances the application of bismuth-based haloperovskite materials in the photocatalytic oxidative coupling reaction of benzylamine by modifying the surface of the material with carbon and nitrogen groups. The materials exhibit excellent catalytic activity and selectivity under long-wavelength light irradiation. Furthermore, the preparation method provided by this invention is simple and reproducible, offering a new technical solution for the application of bismuth-based haloperovskite materials in organic oxidation reactions.

[0110] Based on the test results of Application Examples 1 and 2, and Application Examples 6 to 10, compared with ammonium formate, when ammonium carbamate is used as a carbon-nitrogen precursor for modifying inverse opal Cs3Bi2Br9 and ethyl acetate is used as a solvent for the photocatalytic oxidative coupling reaction of benzylamine, the conversion rate of benzylamine and the selectivity of imine are the highest.

[0111] The applicant declares that the above description is only a specific embodiment of the present invention, but the protection scope of the present invention is not limited thereto. Those skilled in the art should understand that any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope disclosed in the present invention fall within the protection and disclosure scope of the present invention.

Claims

1. A method for preparing an anti-opal bismuth-based haloperovskite material modified with carbon and nitrogen groups, characterized in that, The preparation method includes: A carbon-nitrogen precursor is mixed with an inverse opal bismuth-based haloperovskite material and calcined to obtain the carbon-nitrogen group-modified inverse opal bismuth-based haloperovskite material.

2. The preparation method according to claim 1, characterized in that, The carbon-nitrogen precursors include any one or a combination of at least two of the following: ammonium carbamate, ammonium formate, urea, ammonium citrate, ammonium acetate, ammonium propionate, ammonium oxalate, or ammonium tartrate. And / or, the inverse opal bismuth-based haloperovskite material includes any one or a combination of at least two of inverse opal Cs3Bi2Br9, inverse opal Cs3Bi2Cl9, or inverse opal Cs3Bi2I9.

3. The preparation method according to claim 1 or 2, characterized in that, The average pore size of the inverse opal bismuth-based haloperovskite material is 50 nm to 800 nm.

4. The preparation method according to any one of claims 1 to 3, characterized in that, The mass ratio of the carbon-nitrogen precursor to the inverse opal bismuth-based haloperovskite material is (0.05~200):

1.

5. The preparation method according to any one of claims 1 to 4, characterized in that, The roasting temperature is 300℃~800℃; And / or, the calcination time is 1h to 10h; And / or, the heating rate of the calcination is 1℃ / min to 10℃ / min; And / or, the roasting atmosphere includes any one of air, argon, or nitrogen.

6. A carbon-nitrogen group-modified inverse opal bismuth-based haloperovskite material, characterized in that, The carbon-nitrogen group-modified inverse opal bismuth halide perovskite material is prepared by the preparation method according to any one of claims 1 to 5; The carbon and nitrogen group-modified inverse opal bismuth halide perovskite material includes an inverse opal bismuth halide perovskite matrix and carbon and nitrogen groups modified on the surface of the bismuth halide perovskite matrix.

7. A method for applying a carbon-nitrogen group-modified anti-opal bismuth-based haloperovskite material in the photocatalytic oxidative coupling reaction of benzylamine, characterized in that, The application method includes: The carbon-nitrogen group-modified inverse opal bismuth-based haloperovskite material as described in claim 6 is dispersed with benzylamine in a solvent, and the light source is turned on to initiate the photocatalytic oxidative coupling reaction of benzylamine.

8. The application method as described in claim 7, characterized in that, The amount of the carbon-nitrogen group-modified inverse opal bismuth halide perovskite material added is 3 mg / mL to 5 mg / mL. And / or, the amount of benzylamine added is 0.01 mmol / mL to 0.05 mmol / mL.

9. The application method as described in claim 7 or 8, characterized in that, The solvent includes any one of ethyl acetate, acetonitrile, methanol, ethanol, or 1,4-dioxane.

10. The application method according to any one of claims 7 to 9, characterized in that, The photocatalytic oxidative coupling reaction of benzylamine is carried out under stirring at a speed of 100 rpm to 1000 rpm. And / or, the time for the photocatalytic oxidative coupling reaction of benzylamine is 0.1 h to 48 h; And / or, the light source includes an LED light source or a xenon lamp with a wavelength of 360nm to 800nm.

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