A method for preparing bismuth oxycarbonate nanomaterials by dynamic transformation of light-assisted templates

Abstract

The present invention relates to a method for preparing bismuth oxycarbonate nano-micro materials by dynamic conversion of a light-assisted template. With bismuth salt (or other metal salt) and halide salt as reactants (molar ratio of 1: 3 ~ 3: 1), they are uniformly dissolved in an alcohol-water solvent, stirred at room temperature to synthesize bismuth oxycarbonate solid powder, and dispersed in an alcohol amine solution as a template, illuminated under a carbon dioxide atmosphere, and prepared bismuth oxycarbonate nano-micro materials. Different from existing conventional preparation methods, the advantage of the inventive method is that bismuth oxycarbonate nano-micro materials are obtained at room temperature and pressure, light-assisted template dynamic conversion technology is introduced, the microstructure of bismuth oxycarbonate nano-micro materials is regulated, and specific bismuth oxycarbonate materials with oxygen vacancies, halogen anions and zero-valent metal coexistence structure are obtained, the preparation process is simple, easy to operate, the material composition structure is easy to modulate, and the method is applicable to the preparation of diversified bismuth oxycarbonate nano-micro materials. The present invention can provide bismuth oxycarbonate nano-micro materials with good crystallinity, high yield and uniformity, which have a wide range of practical application values ​​in many fields such as sensors, biomolecule detection, supercapacitors, optical devices, catalysis, lithium ion batteries, medicine, etc.

Description

Technical Field

[0001] The invention belongs to the technical field of nano-micro material preparation, and relates to a method for preparing bismuth oxycarbonate nano-micro material. Background Art

[0002] As an important rare earth metal compound, bismuth oxycarbonate possesses a layered structure composed of alternating ionic layers and is an n-type indirect bandgap semiconductor. It possesses a large surface area, excellent electron transport, photoresponsiveness, thermal stability, and antibacterial properties, making it a valuable material for diverse applications, including sensors, biomolecular detection, supercapacitors, optical devices, catalysis, lithium-ion batteries, and medicine.

[0003] Bismuth oxycarbonate materials are primarily prepared using hydrothermal and solvothermal methods, as exemplified by the national invention patents "A Method for Preparing Bismuth oxycarbonate" (Application No. 201910931436.5), "A Method for Preparing Bismuth oxycarbonate and Its Application" (Application No. 202010249676.X), and "A Method for Preparing Bismuth oxycarbonate-Based Photocatalytic Materials" (Application No. 202111462671.6). Structural manipulation of materials is an effective approach to improving and optimizing their performance, including microstructural manipulation and composite structure construction. For example, the national invention patent "A Bismuth-Bismuth oxycarbonate Heterostructure Photocatalytic Material and Its Preparation Method" (Patent No. ZL201810401641.6) discloses the preparation of a bismuth-bismuth oxycarbonate heterostructure material using bismuth nitro at pressures above 3 MPa and temperatures between 150 and 200°C. Most reported methods for preparing bismuth oxycarbonate require relatively harsh reaction conditions, such as high temperature, high pressure, and an alkaline environment. However, there has been no report on the microstructure-controlled synthesis of bismuth oxycarbonate under room temperature and pressure conditions.

[0004] This paper proposes a method for preparing bismuth oxycarbonate nanomaterials using dynamic transformation of light-assisted templates. This method allows for the preparation of bismuth oxycarbonate nanomaterials with specific microstructures under normal temperature and pressure conditions. The process is simple and controllable. The bismuth oxycarbonate materials synthesized by this method exhibit high purity and crystallinity, good dispersion, and uniform size, and have broad application prospects. Summary of the Invention

[0005] The purpose of the present invention is to provide a simple and easy method for preparing bismuth oxycarbonate nanomaterials, to obtain bismuth oxycarbonate nanomaterials with controllable microstructure, to expand the application prospects of the materials and to improve their performance.

[0006] To achieve the above objectives, the present invention provides a method for preparing bismuth oxycarbonate nanomaterials by dynamic transformation of light-assisted templates, which adopts the following technical methods:

[0007] A bismuth salt and / or other metal salt is dissolved in an alcohol-water solvent, and a halide aqueous solution (the molar ratio of the metal salt to the halide salt is 1:3 to 3:1) is added. The mixture is stirred at room temperature for more than 20 minutes, filtered, washed, and dried to obtain a solid product I. The solid product I is used as a template, ground into a fine powder and dispersed in an alcoholamine solution. A carbon dioxide atmosphere is introduced, and after light irradiation for a period of time, the mixture is filtered, washed, and dried to obtain a bismuth oxycarbonate solid product.

[0008] The above preparation method mainly has the following characteristics:

[0009] The preparation of bismuth oxycarbonate nanomaterials can be carried out at room temperature and pressure. The solid product I is a halide metal oxide, which is dynamically transformed as a template precursor under light assistance to form bismuth oxycarbonate nanostructures.

[0010] The prepared bismuth oxycarbonate nanomaterials include bismuth oxycarbonate, metal-doped bismuth oxycarbonate (the doped metal is a rare earth metal, a transition metal, such as zirconium, cerium, vanadium, iron, cobalt, nickel, copper, chromium, cadmium, etc.), lanthanum oxycarbonate, zirconium oxycarbonate, cerium oxycarbonate, vanadium oxycarbonate or other basic carbonates of different metals.

[0011] The bismuth salt and other metal salts used are metal nitrates, chlorides or sulfates.

[0012] The alcohol-water solvent used is a mixed solvent formed by polyhydroxy alcohols such as ethylene glycol, glycerol or propylene glycol and water.

[0013] The halide salt used is ammonium halide or metal halide, such as ammonium chloride, ammonium bromide, ammonium fluoride, ammonium iodide, potassium iodide, etc.

[0014] The template of the prepared solid product I is a chlorine oxymetalate, a bromide oxymetalate, a fluorine oxymetalate or an iodine oxymetalate.

[0015] The alcoholamine solution used is an aqueous solution or alcohol solution of triethanolammonium, diethanolamine, monoethanolamine, tripropanolamine, diisopropanolamine or tromethamine.

[0016] The carbon dioxide atmosphere used is air, carbon dioxide, a carbon dioxide mixture or a soluble salt containing carbonate such as sodium carbonate or sodium bicarbonate. The preferred reaction system pressure is normal pressure.

[0017] The light source used is a mercury lamp, a xenon lamp, sunlight or indoor natural light, and the illumination time is more than 2 hours.

[0018] Unlike other preparation methods, the method provided by the present invention can produce bismuth oxycarbonate nanomaterials at room temperature and pressure. It utilizes dynamic transformation and structural replication of bismuth oxycarbonate nanomaterial templates. Light irradiation assists in the manipulation of the bismuth oxycarbonate material's microstructure, resulting in a specific structure characterized by the coexistence of oxygen vacancies, halogen anions, and zero-valent metals. This method is also applicable to the preparation of other metal basic carbonate nanomaterials. This preparation method is simple and easy to operate and is applicable to bismuth oxycarbonate nanomaterials with diverse compositions. Its structure and properties are easily adjustable, making it potentially suitable for a wide range of applications. BRIEF DESCRIPTION OF THE DRAWINGS

[0019] Figure 1 This is a SEM image of the bismuth oxybromide template material prepared in an example of the present invention;

[0020] Figure 2 This is a SEM image of the bismuth oxycarbonate material prepared in an example of the present invention;

[0021] Figure 3 The XRD patterns of bismuth oxybromide and bismuth oxycarbonate materials prepared in the examples of the present invention are shown below:

[0022] Figure 4 This is the XPS graph of the bismuth oxycarbonate material prepared in this example of the present invention. DETAILED DESCRIPTION

[0023] The present invention will be further described below with reference to the examples, but the present invention is not limited to the following examples.

[0024] Example 1

[0025] 0.4851 g of bismuth nitrate was dissolved in 50 ml of ethylene glycol-water (volume ratio of 1:1), and an aqueous solution containing 0.0979 g of ammonium bromide was added. After stirring at room temperature for 20 minutes, the mixture was filtered, washed with water and ethanol, and dried at 60°C to obtain a solid product, bismuth oxybromide, which was ground into a fine powder and dispersed in a triethanolamine solution. Carbon dioxide was introduced and irradiated with a xenon lamp for 4 hours. The mixture was filtered, washed with water and ethanol, and dried at 60°C to obtain bismuth oxycarbonate.

[0026] Example 2

[0027] 0.9702 g of bismuth nitrate was dissolved in 50 ml of glycerol-water (volume ratio of 1:1), and an aqueous solution containing 0.0979 g of ammonium bromide was added. After stirring at room temperature for 20 minutes, the mixture was filtered, washed with water and ethanol, and dried at 60°C to obtain a solid product, bismuth oxybromide, which was ground into a fine powder and dispersed in a triethanolamine solution. Carbon dioxide was introduced and irradiated with a xenon lamp for 6 hours. The mixture was filtered, washed with water and ethanol, and dried at 60°C to obtain bismuth oxycarbonate.

[0028] Example 3

[0029] 0.4851 g of bismuth nitrate was dissolved in 50 ml of ethylene glycol-water (volume ratio of 1:1), and an aqueous solution containing 0.1660 g of potassium iodide was added. After stirring at room temperature for 30 minutes, the mixture was filtered, washed with water and ethanol, and dried at 60°C to obtain a solid product, bismuth oxyiodide, which was ground into a fine powder and dispersed in a tripropanolamine solution. Carbon dioxide was introduced and irradiated with a xenon lamp for 6 hours. The mixture was filtered, washed with water and ethanol, and dried at 60°C to obtain bismuth oxycarbonate.

[0030] Example 4

[0031] 0.4851 g of bismuth nitrate and 0.0020 g of lanthanum chloride heptahydrate were dissolved in 50 ml of ethylene glycol-water (volume ratio of 1:1), and an aqueous solution containing 0.1660 g of potassium iodide was added. After stirring at room temperature for 30 minutes, the mixture was filtered, washed with water and ethanol, and dried at 60°C to obtain a solid product, lanthanum-doped bismuth oxyiodide. The solid product was ground into a fine powder and dispersed in a triethanolamine solution. Carbon dioxide was introduced and irradiated with a xenon lamp for 6 hours. The mixture was filtered, washed with water and ethanol, and dried at 60°C to obtain lanthanum-doped bismuth oxycarbonate.

Claims

1. A method for preparing bismuth oxycarbonate nanomaterials by dynamic transformation of light-assisted templates, characterized in that: The method comprises the following steps: dissolving a bismuth salt and / or other metal salt in an alcohol-water solvent, adding a halide aqueous solution with a molar ratio of the metal salt to the halide being 1:3 to 3:1, stirring at room temperature for more than 20 minutes, filtering, washing, and drying to obtain a solid product I; using the solid product I as a template, grinding it into a fine powder and dispersing it in an alcoholamine solution, introducing a carbon dioxide atmosphere, irradiating it with light for a period of time, filtering, washing, and drying to obtain a final solid product, which is a bismuth oxycarbonate nanomaterial; The prepared bismuth oxycarbonate nanomaterials are bismuth oxycarbonate with a special microstructure, namely the coexistence of oxygen vacancies, halogen ions, and zero-valent metals, as well as metal-doped bismuth oxycarbonate and basic carbonates of other different metals; The light irradiation time is more than 2 hours, and the irradiation light source includes a mercury lamp or a xenon lamp containing ultraviolet light, ultraviolet-visible light, ultraviolet-visible-infrared light, sunlight or indoor natural light.

2. The method for preparing bismuth oxycarbonate nanomaterials by dynamic transformation of light-assisted templates according to claim 1, characterized in that: The bismuth salt and / or other metal salts include nitrates, chlorides or sulfates of the metals mentioned in claim 1.

3. The method for preparing bismuth oxycarbonate nanomaterials by dynamic transformation of light-assisted templates according to claim 1, characterized in that: The alcohol-water solvent includes a mixed solvent of one or more of ethylene glycol, glycerol, propylene glycol and water.

4. The method for preparing bismuth oxycarbonate nanomaterials by dynamic transformation of light-assisted templates according to claim 1, characterized in that: The halide salts include ammonium halides or metal halides.

5. The method for preparing bismuth oxycarbonate nanomaterials by dynamic transformation of light-assisted templates according to claim 1, characterized in that: The solid product I is a template for synthesizing bismuth oxycarbonate materials, including chlorine oxymetallates, bromide oxymetallates, fluoride oxymetallates or iodine oxymetallates of the metal mentioned in claim 1.

6. The method for preparing bismuth oxycarbonate nanomaterials by dynamic transformation of light-assisted templates according to claim 1, characterized in that: The alcohol amine solution includes one or more mixed solutions of triethanolamine, diethanolamine, tripropanolamine, diisopropanolamine and tromethamine aqueous solutions.

7. The method for preparing bismuth oxycarbonate nanomaterials by dynamic transformation of light-assisted templates according to claim 1, characterized in that: The pressure of the reaction system after the carbon dioxide atmosphere was introduced was 0.1-0.2 MPa.

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