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CN-121607168-B - F. Pd modified single crystal BiVO4Photocatalyst and synergistic H production by photocatalytic degradation of glyphosate2O2Application in (a)

CN121607168BCN 121607168 BCN121607168 BCN 121607168BCN-121607168-B

Abstract

The invention provides F, pd modified monocrystal BiVO 4 photocatalyst and application thereof in the synergistic production of H 2 O 2 by photocatalytic degradation of glyphosate. Dispersing single crystal BiVO 4 powder in deionized water solution to obtain suspension, adding fluoride solution into the suspension, stirring for a certain time under illumination, washing and drying to obtain a photocatalyst (BiVO 4 -F-110) with F ‑ modified on (110) crystal face of enriched photohole of single crystal BiVO 4 , dispersing BiVO 4 -F-110 into methanol aqueous solution, adding a certain amount of palladium chloride aqueous solution, continuously introducing Ar, removing dissolved O 2 in the suspension, then carrying out illumination treatment under stirring condition, washing and drying the obtained precipitate after illumination is finished to obtain the photocatalyst. The F ions can be selectively modified on the cavity-rich crystal face of the monocrystal bismuth vanadate to promote the adsorption of glyphosate so as to effectively capture photo-generated cavities, and the Pd-loaded (010) crystal face can effectively enhance the reduction of O 2 to produce H 2 O 2 so as to realize the synergistic effect of pollutant degradation and H 2 O 2 synthesis.

Inventors

  • HUANG YINGPING
  • SHI HAIYANG
  • DING SHAOQI
  • HUANG DI

Assignees

  • 三峡大学

Dates

Publication Date
20260508
Application Date
20260202

Claims (10)

  1. 1. A preparation method of F, pd modified single crystal BiVO 4 photocatalyst is characterized by comprising the following steps: (1) Dispersing single crystal BiVO 4 powder in an aqueous solution to prepare a suspension; (2) Adding a proper amount of F ion source solution into the suspension obtained in the step (1), and stirring and uniformly mixing under illumination; (3) After the illumination of the step (2) is finished, washing and drying the obtained precipitate to obtain F - modified on a (110) crystal face of a monocrystal bismuth vanadate enriched light cavity to form a BiVO 4 -F-110 photocatalyst; (4) Dispersing the BiVO 4 -F-110 photocatalyst prepared in the step (3) into a methanol aqueous solution, adding a palladium source solution, continuously introducing Ar, removing O 2 dissolved in the suspension, and carrying out illumination treatment under the stirring condition; (5) And (3) after the illumination of the step (4) is finished, washing and drying the obtained precipitate to obtain the monocrystal bismuth vanadate hole crystal face modified F and electron crystal face modified Pd photocatalyst Pd-010-BiVO 4 -F-110.
  2. 2. The preparation method of F, pd modified single crystal BiVO 4 photocatalyst according to claim 1, wherein F ion source is organic fluoride or inorganic fluoride, the organic fluoride is selected from any one of triethylamine, tri-hydrofluoric acid, tetrabutylammonium fluoride, tetramethyl ammonium fluoride and tetraethyl ammonium fluoride; the inorganic fluorine salt is selected from NH 4 HF 2 、NH 4 F, HF or KF.
  3. 3. The method for preparing F, pd modified single crystal BiVO 4 photocatalyst according to claim 2, wherein the concentration of the F ion source solution is 0.01-0.5M.
  4. 4. The method for preparing the F, pd modified single crystal BiVO 4 photocatalyst according to claim 1, wherein in the step (2), the illumination reaction is 0.1-8. 8h, and the light source used for illumination is any one of a xenon lamp, a mercury lamp, a metal halogen lamp or an LED lamp.
  5. 5. The method for preparing F, pd modified single crystal BiVO 4 photocatalyst according to claim 1, wherein the palladium source in step (4) comprises soluble Pd salt in PdCl 2 、Pd(NO 3 ) 2 、PdSO 4 、Pd(OAc) 2 、Na 2 PdCl 4 、K 2 PdCl 6 、(NH 4 ) 2 PdCl 6 , and the palladium loading is 0.01-5 wt%.
  6. 6. The method for preparing the F, pd modified single crystal BiVO 4 photocatalyst according to claim 1, wherein the illumination reaction in the step (4) is 0.1-8 h, and the illumination is any one of a xenon lamp, a mercury lamp, a metal halogen lamp or an LED lamp.
  7. 7. A F, pd modified single crystal BiVO 4 photocatalyst is characterized in that the photocatalyst is prepared by adopting the method of any one of claims 1-6, wherein bismuth vanadate is a Pd nanoparticle loaded on a hole-rich crystal face (110) and selectively modified F - and an electron-rich crystal face (010).
  8. 8. The use of F, pd modified single crystal BiVO 4 photocatalyst according to claim 7 in catalyzing the reduction of O 2 to H 2 O 2 .
  9. 9. The use of F, pd modified single crystal BiVO 4 photocatalyst according to claim 8 for the catalytic degradation of glyphosate in H 2 O 2 production.
  10. 10. The use according to claim 9, wherein F, pd modifies the single crystal BiVO 4 photocatalyst to form H 2 O 2 by photocatalytic oxygen reduction in a solution containing glyphosate.

Description

F. Pd modified single crystal BiVO 4 photocatalyst and application thereof in synergistic production of H 2O2 by photocatalytic degradation of glyphosate Technical Field The invention belongs to the technical field of preparation of photocatalytic materials and environmental management, and particularly relates to a monocrystal BiVO 4 photocatalyst with crystal face selective modification and a preparation method thereof. The catalyst selectively modifies F ions on a monocrystalline bismuth vanadate hole-rich (110) crystal face to promote photo-generated hole oxidation and degradation of glyphosate, and simultaneously selectively loads Pd nano particles on an electron-rich (010) crystal face to enhance O 2 for reduction to generate H 2O2, so that high-efficiency synergistic pollution control and green chemical H 2O2 synthesis are realized. Background Glyphosate is one of the widely used herbicides worldwide, and remains in the natural environment after use, posing a serious threat to the ecological environment and human health. In contrast to traditional advanced oxidation processes such as Fenton, adsorption, ozone oxidation, etc., emerging photocatalytic technologies can utilize photocatalysts to activate molecular oxygen or H 2 O to form reactive oxygen species, converting solar energy into chemical energy to promote contaminant degradation. However, the conventional single photocatalyst has the problems of high carrier recombination rate, weak interaction with a pollutant molecular interface, low reaction efficiency and the like. The single crystal BiVO 4 is widely studied because of its proper energy band structure capable of effectively utilizing visible light absorption and excellent crystal face exposure to effectively avoid the in vivo recombination of photogenerated carriers to realize space separation. However, the pure BiVO 4 crystal is composed of Bi-O tetrahedron and V-O octahedron, and the surface metal (Bi and V) and oxygen form covalent bonding action to make the surface lack effective catalytic active sites, so that the interfacial adsorption effect on H 2 O and oxygen molecules is weak. In general, precious metal (such as Pd, pt, au and the like) modification can effectively improve the H 2O2 reduction efficiency of O 2, but alcohol small molecules are used as a sacrificial agent to capture photo-generated holes, so that the utilization efficiency of a photocatalysis reaction is reduced, and anion modification (such as F -) can regulate and control the surface property to a certain extent, improve the adsorption and activation of the surface H 2 O, but single modification is difficult to realize the synergy of H 2O2 generation and pollutant degradation at the same time. Therefore, a BiVO 4 photocatalyst with crystal face selectively modified is developed, has high-efficiency H 2O2 synthesis and glyphosate degradation capacity, and has important application value. Disclosure of Invention The invention solves the problems of low carrier utilization efficiency, weak interface effect of O 2 molecules and a photocatalyst, poor degradation efficiency of glyphosate and insufficient yield of H 2O2 of the existing BiVO 4 photocatalyst, provides a Pd-010-BiVO 4 -F-110 photocatalyst selectively modified by a photoinduction synthetic crystal face, enhances adsorption and oxidation of the glyphosate by selectively modifying a cavity (110) -rich crystal face of the Pd-010-BiVO 4 -F-110 photocatalyst through F -, and promotes O 2 reduction to generate H 2O2 on an electron-rich (010) -rich crystal face of the Pd nano-particle modified metal Pd nano-particle so as to realize synergistic effect. A preparation method of F, pd modified monocrystal BiVO 4 photocatalyst comprises the steps of preparing a monocrystal BiVO 4 photocatalyst with crystal face selectively modified, namely Pd-010-BiVO 4 -F-110, wherein monocrystal BiVO 4 is used as a main body, a (110) crystal face of the monocrystal BiVO 4 photocatalyst is modified by F - to form BiVO 4 -F-110, pd nano particles are loaded on a (010) crystal face of the monocrystal BiVO 4 photocatalyst, F ion modification amount is 0.01-10wt% of the mass of the BiVO 4, and Pd loading amount is 0.01-5wt%. The method comprises the following steps: (1) Dispersing single crystal BiVO 4 powder in an aqueous solution to prepare a uniformly dispersed suspension; (2) Adding a proper amount of F ion source solution into the suspension obtained in the step (1), and stirring for a certain time under illumination; (3) After the illumination of the step (2) is finished, washing and drying the obtained precipitate to obtain a photocatalyst formed by F - modified on a photo-cavity crystal face of the monocrystal bismuth vanadate, namely a BiVO 4 -F-110 photocatalyst; (4) Dispersing the BiVO 4 -F-110 photocatalyst prepared in the step (3) into a methanol aqueous solution, adding a certain amount of palladium source solution, continuously introducing Ar, removing O 2 dissolved in th