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CN-121972205-A - Nonmetal plasmon heterojunction material, preparation method and application thereof, and method for preparing p-aminophenol by reduction of p-nitrophenol

CN121972205ACN 121972205 ACN121972205 ACN 121972205ACN-121972205-A

Abstract

The invention relates to the technical field of photocatalysts, in particular to a nonmetallic plasmon heterojunction material, a preparation method and application thereof, and a method for preparing p-aminophenol by reducing p-nitrophenol. The nonmetallic plasmon heterojunction material provided by the invention comprises a C 3 N 4 nano-sheet and a WO 3‑x nano-sheet (x is 0.1-0.3) positioned on the surface of the C 3 N 4 nano-sheet. The spectral response range of the nonmetallic plasmon heterojunction material in the visible-near infrared region can be effectively expanded due to the local surface plasmon property of WO 3‑x , and the light absorption efficiency of the nonmetallic plasmon heterojunction material is remarkably enhanced. The nonmetal plasmon heterojunction material provided by the invention can realize efficient reduction of p-nitrophenol based on the synergistic effect of the interface heterojunction, the built-in electric field and the oxygen vacancy, has high selectivity, has excellent photocatalytic activity for reduction of p-nitrophenol, and has excellent stability of the photocatalytic activity.

Inventors

  • GUO YANZHEN
  • ZHANG SHOUREN
  • YANG BAOCHENG
  • HUANG XIN
  • CHANG BINBIN
  • LIU HUILI
  • WU DONGHAI

Assignees

  • 黄河科技学院

Dates

Publication Date
20260505
Application Date
20260311

Claims (10)

  1. 1. The nonmetallic plasmon heterojunction material is characterized by comprising a C 3 N 4 nano sheet and a WO 3-x nano sheet positioned on the surface of the C 3 N 4 nano sheet, wherein x in the WO 3-x nano sheet is 0.1-0.3.
  2. 2. The nonmetallic plasmon heterojunction material of claim 1, wherein the mass fraction of WO 3-x in the nonmetallic plasmon heterojunction material is 4.4-50.9%.
  3. 3. The nonmetallic plasmon heterojunction material of claim 1, wherein the thickness of the C 3 N 4 nano-sheet is 1-5 nm; The thickness of the WO 3-x nano-plate is 10-40 nm.
  4. 4. The method for preparing the nonmetallic plasmon heterojunction material according to any one of claims 1-3, characterized by comprising the following steps: Mixing a water-soluble tungstic acid source, inorganic strong acid, a C 3 N 4 nano-sheet, organic acid and water, and performing acidification hydrolysis and in-situ growth to obtain a precursor, wherein the precursor comprises a C 3 N 4 nano-sheet and a WO 3 nano-sheet in-situ grown on the C 3 N 4 nano-sheet; and carrying out thermal reduction treatment on the precursor in a hydrogen-containing atmosphere to obtain the nonmetallic plasmon heterojunction material.
  5. 5. The method according to claim 4, wherein the ratio of the amount of the water-soluble tungstic acid source substance to the mass of the C 3 N 4 nano-sheet is 0.5 to 1.5 mmol/0.1 to 1.6g; The inorganic strong acid comprises one or more of hydrochloric acid, sulfuric acid, nitric acid and hydrobromic acid; The molar ratio of the water-soluble tungstic acid source to the inorganic strong acid is 0.01-0.03:0.5-4; the organic acid comprises one or more of oxalic acid, malonic acid, succinic acid, citric acid and ethylenediamine tetraacetic acid; the molar ratio of the water-soluble tungstic acid source to the organic acid is 1:0.5-2.
  6. 6. The method according to claim 4 or 5, wherein the temperature of the acid hydrolysis and in-situ growth is 70-100 ℃ and the time is 0.5-3 h.
  7. 7. The preparation method of the hydrogen-containing gas according to claim 4, wherein the hydrogen-containing gas atmosphere comprises a mixed gas of hydrogen and protective gas or hydrogen, the volume ratio of the hydrogen to the protective gas in the mixed gas is 5-10:90-95, and the flow rate of the hydrogen-containing gas atmosphere is 10-100 mL/min; The temperature of the thermal reduction treatment is 200-500 ℃ and the time is 1-5 h.
  8. 8. The use of the nonmetallic plasmon heterojunction material of any one of claims 1-3 or the nonmetallic plasmon heterojunction material prepared by the preparation method of any one of claims 4-7 as a photocatalyst.
  9. 9. The use according to claim 8, wherein the use comprises the preparation of para-aminophenol by photocatalytic reduction of para-nitrophenol.
  10. 10. A method for preparing p-aminophenol by reducing p-nitrophenol, which is characterized by comprising the following steps: Mixing a p-nitrophenol solution and a catalyst, and carrying out reduction reaction under illumination condition to obtain p-aminophenol, wherein the catalyst is the non-metal plasmon heterojunction material according to any one of claims 1-3 or the non-metal plasmon heterojunction material prepared by the preparation method according to any one of claims 4-7, and the wavelength of illumination is more than or equal to 420nm.

Description

Nonmetal plasmon heterojunction material, preparation method and application thereof, and method for preparing p-aminophenol by reduction of p-nitrophenol Technical Field The invention relates to the technical field of photocatalysts, in particular to a nonmetallic plasmon heterojunction material, a preparation method and application thereof, and a method for preparing p-aminophenol by reducing p-nitrophenol. Background P-nitrophenol, a typical aromatic nitro compound, has significant biotoxicity, high environmental persistence and bioaccumulation. On the one hand, p-nitrophenol has specific toxic action on liver and kidney organs after being absorbed by organisms. On the other hand, the nitro group and the phenolic hydroxyl group in the nitrophenol molecular structure jointly act to endow the nitrophenol with higher chemical stability, so that the nitrophenol is difficult to effectively decompose under natural conditions, and therefore, the nitrophenol is remained in water and soil for a long time. The current method for treating p-nitrophenol mainly comprises physical adsorption separation technology, chemical oxidation technology and biodegradation method. The adsorption separation technology mainly utilizes the high specific surface area of porous materials such as active carbon, biochar or synthetic resin, and realizes enrichment and phase transfer of p-nitrophenol in water phase through mechanisms such as Van der Waals force, pi-pi interaction, and the like. The chemical oxidation process is characterized in that p-nitrophenol is mineralized into carbon dioxide, water and inorganic ions through electrochemistry, fenton reaction and the like, and the method can radically eliminate the toxicity of the p-nitrophenol, but is complex in operation and unsuitable for large-scale application. Biodegradation is an environmentally friendly alternative but depends on specific functional microorganisms. Reduction of p-nitrophenol to less toxic p-aminophenol, the conversion product being favorable to further degradation by microorganisms in the environment, is a potential strategy for removing p-nitrophenol. For example, the photocatalytic reduction of p-nitrophenol utilizes solar energy as a driving force, and the p-nitrophenol can be reduced into the p-aminophenol at normal temperature and normal pressure, so that the method has the advantages of environment friendliness, sustainability and high efficiency. However, catalyzing the reduction of p-nitrophenols with a single semiconductor typically requires the additional introduction of NaBH 4 as a hole sacrificial agent to inhibit electron-hole recombination. Disclosure of Invention In view of the above, the invention aims to provide a nonmetallic plasmon heterojunction material, a preparation method and application thereof, and a method for preparing p-aminophenol by reducing p-nitrophenol. The nonmetallic plasmon heterojunction material provided by the invention can be independently used for catalyzing the reduction reaction of p-nitrophenol, does not need to introduce a hole sacrificial agent, and has high photocatalytic activity. In order to achieve the above object, the present invention provides the following technical solutions: The invention provides a nonmetallic plasmon heterojunction material which comprises a C 3N4 nano sheet and a WO 3-x nano sheet positioned on the surface of the C 3N4 nano sheet, wherein x in the WO 3-x nano sheet is 0.1-0.3. Preferably, the mass fraction of WO 3-x in the nonmetallic plasmon heterojunction material is 4.4-50.9%. Preferably, the thickness of the C 3N4 nano-sheet is 1-5 nm; The thickness of the WO 3-x nano-plate is 10-40 nm. The invention also provides a preparation method of the nonmetallic plasmon heterojunction material, which comprises the following steps: Mixing a water-soluble tungstic acid source, inorganic strong acid, a C 3N4 nano-sheet, organic acid and water, and performing acidification hydrolysis and in-situ growth to obtain a precursor, wherein the precursor comprises a C 3N4 nano-sheet and a WO 3 nano-sheet in-situ grown on the C 3N4 nano-sheet; and carrying out thermal reduction treatment on the precursor in a hydrogen-containing atmosphere to obtain the nonmetallic plasmon heterojunction material. Preferably, the ratio of the mass of the water-soluble tungstic acid source to the mass of the C 3N4 nano-sheet is 0.5-1.5 mmol/0.1-1.6 g; The inorganic strong acid comprises one or more of hydrochloric acid, sulfuric acid, nitric acid and hydrobromic acid; The molar ratio of the water-soluble tungstic acid source to the inorganic strong acid is 0.01-0.03:0.5-4; the organic acid comprises one or more of oxalic acid, malonic acid, succinic acid, citric acid and ethylenediamine tetraacetic acid; the molar ratio of the water-soluble tungstic acid source to the organic acid is 1:0.5-2. Preferably, the temperature of the acidification hydrolysis and in-situ growth is 70-100 ℃ and the time is 0.5-3 h. Preferably,