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CN-122006775-A - Bismuth-silver composite micro-nano material for water treatment and preparation method thereof

CN122006775ACN 122006775 ACN122006775 ACN 122006775ACN-122006775-A

Abstract

The scheme relates to a bismuth-silver composite micro-nano material for water treatment and a preparation method thereof, wherein functional graphene quantum dots are prepared by firstly taking citric acid, urea and ethylenediamine as raw materials to prepare N-GQDs-NH 2 quantum dots, then introducing phosphate groups and porphyrin groups through covalent bonding and pi-pi stacking, mixing a bismuth source, a tungsten source and prepared functional graphene quantum dot dispersion liquid, carrying out ultrasonic treatment to obtain a precursor solution A, dissolving a silver source and a vanadium source in water, and dropwise adding the silver source and the vanadium source into the solution A for hydrothermal reaction. According to the invention, the Bi 2 WO 6 /AgVO 3 compound is prepared by taking the functional graphene quantum dots as bridges, and the Bi 2 WO 6 and the AgVO 3 are successfully compounded to form a stable photocatalyst with micro-nano scale, so that the formed ternary compound has high catalytic activity on printing and dyeing molecules and good cycling stability.

Inventors

  • ZHOU HUI
  • JIN DANGQIN
  • Xiao Gali
  • QIAN CHEN
  • CHEN LIPING

Assignees

  • 扬州工业职业技术学院

Dates

Publication Date
20260512
Application Date
20260204

Claims (7)

  1. 1. The preparation method of the bismuth-silver composite micro-nano material for water treatment is characterized by comprising the following steps: S1, functional graphene quantum dot S1-1, dissolving citric acid, urea and ethylenediamine in water, and preparing N-GQDs-NH 2 quantum dots with nitrogen doping and rich surface amino groups by a microwave-assisted method; s1-2, dispersing N-GQDs-NH 2 quantum dots in PBS buffer solution, then adding EDC and NHS to activate 30 min, adding 2-carboxyethyl phosphonic acid into a reaction system, reacting 24-h at room temperature in a dark place under the protection of nitrogen, dialyzing, and freeze-drying to obtain N-GQDs-PO 3 quantum dots; S1-3, re-dispersing N-GQDs-PO 3 quantum dots in a PBS buffer solution to form a stable suspension, dissolving tetracarboxyl phenyl porphyrin in the PBS buffer solution, slowly dripping the suspension into the suspension, continuously stirring for 4 hours after dripping, performing ultrafiltration purification under the protection of light and nitrogen in the whole process, obtaining functional graphene quantum dots, dispersing the functional graphene quantum dots in an aqueous solution, and preserving the functional graphene quantum dots in the light for later use; S2, preparing a ternary precursor solution, namely mixing a bismuth source and a tungsten source with the functional graphene quantum dot dispersion liquid prepared in the step S1, and performing ultrasonic treatment to obtain a precursor solution A; S3, preparing a ternary complex, namely dissolving a silver source and a vanadium source in water to obtain a solution B, dropwise adding the solution B into the solution A, regulating the pH value to 4.0-6.0, ageing for 2 hours at room temperature, transferring into a hydrothermal reaction kettle, and reacting for 6-12 hours at 150-180 ℃; S4, post-treatment of the product, namely centrifuging, washing and drying the product after the reaction is finished to obtain the bismuth-silver composite micro-nano material.
  2. 2. The preparation method of the bismuth-silver composite micro-nano material for water treatment according to claim 1, wherein the preparation process of the N-GQDs-NH 2 quantum dot is characterized in that citric acid, urea and ethylenediamine are mixed and dissolved in deionized water according to the mass ratio of 2:3:1, transferred to a microwave reaction kettle, reacted for 10min at 200 ℃, naturally cooled, dialyzed and freeze-dried to obtain the bismuth-silver composite micro-nano material.
  3. 3. The preparation method of the bismuth-silver composite micro-nano material for water treatment according to claim 1, wherein the mass ratio of the N-GQDs-NH 2 quantum dot to the 2-carboxyethyl phosphonic acid is 1:2-3, and the mass ratio of the N-GQDs-PO 3 quantum dot to the tetracarboxyphenyl porphyrin is 1:0.4-0.8.
  4. 4. The method for preparing the bismuth-silver composite micro-nano material for water treatment according to claim 1, wherein the bismuth source and the tungsten source are bismuth nitrate pentahydrate and sodium tungstate respectively, and the molar ratio is 2:1.
  5. 5. The preparation method of the bismuth-silver composite micro-nano material for water treatment according to claim 1, wherein the concentration of the functional graphene quantum dot dispersion liquid is 1-5 mg/mL, and the ratio of the solute mass to the total mass of the bismuth source and the tungsten source is 0.1-0.3:1.
  6. 6. The method for preparing the bismuth-silver composite micro-nano material for water treatment according to claim 1, wherein the silver source is silver nitrate, the vanadium source is ammonium metavanadate, and the molar ratio of the silver source to the bismuth source is 0.1-0.5:1.
  7. 7. The bismuth-silver composite micro-nano material for water treatment prepared by the preparation method according to any one of claims 1 to 6.

Description

Bismuth-silver composite micro-nano material for water treatment and preparation method thereof Technical Field The invention relates to the technical field of water treatment nano materials, in particular to a bismuth-silver composite micro-nano material for water treatment and a preparation method thereof. Background AgVO 3 has a forbidden bandwidth of about 2.20 eV, is a silver-based semiconductor photocatalyst with good visible light absorption performance, is used for degrading organic pollutants, and has potential in treating dye wastewater. The application core is to utilize the photocatalysis technology, which is an efficient, green and reusable treatment method. Recently, as for bismuth-based semiconductor materials, because of their unique physicochemical properties, excellent biocompatibility and low toxicity, synthetic methods (e.g., hydrothermal method) thereof have been relatively mature, and many bismuth-based semiconductors such as bisx, bi 2WO6、BiVO4、Bi2MoO6 have been successfully prepared, wherein Bi 2WO6 is a typical layered perovskite-type semiconductor having a band gap of about 2.7, 2.7 eV, a stable crystal structure and good photocatalytic activity, but a limited absorption range of visible light, and quantum efficiency has been desired to be improved. The heterojunction is constructed by compounding Bi 2WO6 and AgVO 3, charge separation can be promoted through energy band matching, catalytic performance superior to that of a single component is expected to be obtained, and however, the compounding research of the two substances is relatively less. Disclosure of Invention Aiming at the defects in the prior art, the invention is expected to combine the functional graphene quantum dots, and a Bi 2WO6/AgVO3 composite photocatalyst with high stability and high catalytic activity is constructed on the surface of the Bi 2WO6/AgVO3 composite photocatalyst. In order to achieve the above purpose, the present invention provides the following technical solutions: the preparation method of the bismuth-silver composite micro-nano material for water treatment comprises the following steps: S1, functional graphene quantum dot S1-1, dissolving citric acid, urea and ethylenediamine in water, and preparing N-GQDs-NH 2 quantum dots with nitrogen doping and rich surface amino groups by a microwave-assisted method; s1-2, dispersing N-GQDs-NH 2 quantum dots in PBS buffer solution, then adding EDC and NHS to activate 30 min, adding 2-carboxyethyl phosphonic acid into a reaction system, reacting 24-h at room temperature in a dark place under the protection of nitrogen, dialyzing, and freeze-drying to obtain N-GQDs-PO 3 quantum dots; S1-3, re-dispersing N-GQDs-PO 3 quantum dots in a PBS buffer solution to form a stable suspension, dissolving tetracarboxyl phenyl porphyrin in the PBS buffer solution, slowly dripping the suspension into the suspension, continuously stirring for 4 hours after dripping, performing ultrafiltration purification under the protection of light and nitrogen in the whole process, obtaining functional graphene quantum dots, dispersing the functional graphene quantum dots in an aqueous solution, and preserving the functional graphene quantum dots in the light for later use; S2, preparing a ternary precursor solution, namely mixing a bismuth source and a tungsten source with the functional graphene quantum dot dispersion liquid prepared in the step S1, and performing ultrasonic treatment to obtain a precursor solution A; S3, preparing a ternary complex, namely dissolving a silver source and a vanadium source in water to obtain a solution B, dropwise adding the solution B into the solution A, regulating the pH value to 4.0-6.0, ageing for 2 hours at room temperature, transferring into a hydrothermal reaction kettle, and reacting for 6-12 hours at 150-180 ℃; S4, post-treatment of the product, namely centrifuging, washing and drying the product after the reaction is finished to obtain the bismuth-silver composite micro-nano material. Further, the preparation process of the N-GQDs-NH 2 quantum dot specifically comprises the steps of mixing and dissolving citric acid, urea and ethylenediamine in deionized water according to a mass ratio of 2:3:1, transferring to a microwave reaction kettle, reacting for 10min at 200 ℃, naturally cooling, dialyzing, and freeze-drying. Further, the mass ratio of the N-GQDs-NH 2 quantum dots to the 2-carboxyethyl phosphonic acid is 1:2-3, and the mass ratio of the N-GQDs-PO 3 quantum dots to the tetracarboxylic phenyl porphyrin is 1:0.4-0.8. Further, the bismuth source and the tungsten source are bismuth nitrate pentahydrate and sodium tungstate respectively, and the molar ratio is 2:1. Further, the concentration of the functional graphene quantum dot dispersion liquid is 1-5 mg/mL, and the total mass ratio of the solute mass to the bismuth source and the tungsten source is 0.1-0.3:1. Further, the silver source is silver nitrate, the vanadium source is ammonium me