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CN-117282450-B - Silver chloride/silver-copper iron titanium oxide composite material and preparation method and application thereof

CN117282450BCN 117282450 BCN117282450 BCN 117282450BCN-117282450-B

Abstract

The invention provides a preparation method of a silver chloride/silver-copper iron titanium oxide composite material, which comprises the following steps of S1, dissolving citric acid in an ethanol solution to obtain a mixed solution A, S2, dropwise adding a butyl tetratitanate solution into the mixed solution A to obtain a mixed solution B, S3, adding copper nitrate and ferric nitrate into deionized water to obtain a mixed solution C, S4, dropwise adding the mixed solution B into the mixed solution C, adjusting pH to obtain a mixed solution D, S5, carrying out solvothermal reaction on the mixed solution D to obtain a precipitate, S6, washing, centrifuging, drying and grinding the precipitate to obtain a copper iron titanium oxide material, S7, weighing silver nitrate and copper iron titanium oxide material, adding the silver nitrate and the copper iron titanium oxide material into a quartz reaction tube, adding deionized water, carrying out photo-deposition by using a mercury lamp to obtain a mixed solution, S8, dropwise adding a sodium chloride solution into the mixed solution to obtain a mixture, and S9, carrying out centrifugal washing, drying and grinding on the mixture to obtain the silver chloride-copper iron titanium oxide composite material.

Inventors

  • YU SHUILI
  • Ji Xingli
  • XU YING
  • ZHANG WEI
  • BAI CHENGLING

Assignees

  • 同济大学

Dates

Publication Date
20260505
Application Date
20230625

Claims (8)

  1. 1. The preparation method of the silver chloride/silver-copper iron titanium oxide composite material is characterized by comprising the following steps of: Step S1, dissolving citric acid in an ethanol solution, stirring and carrying out ultrasonic treatment to obtain a mixed solution A; Step S2, dripping tetrabutyl titanate solution into the mixed solution A, stirring and carrying out ultrasonic treatment to obtain a mixed solution B; step S3, adding copper nitrate and ferric nitrate into deionized water, stirring and uniformly mixing to obtain a mixed solution C; Step S4, dropwise adding the mixed solution B into the mixed solution C, adjusting the pH value, and vigorously stirring to obtain a mixed solution D; s5, performing solvothermal reaction on the mixed solution D to obtain a precipitate; s6, washing, centrifuging, drying and grinding the precipitate to obtain a copper-iron-titanium oxide material; S7, weighing silver nitrate and the copper-iron-titanium oxide material, adding the silver nitrate and the copper-iron-titanium oxide material into a quartz reaction tube, adding deionized water, uniformly stirring, and performing photo-deposition by using a mercury lamp to obtain a mixed solution; step S8, dropwise adding a sodium chloride solution into the mixed solution, and stirring to obtain a mixture; step S9, the mixture is centrifuged, washed, dried and ground to obtain a silver chloride/silver-copper iron titanium oxide composite material, Wherein in the step S1, the volume of the ethanol solution is 15ml-30ml, In the step S3, the volume of the deionized water is 60ml-75ml, The volume ratio of the ethanol solution to the deionized water in the step S3 is 1:2-1:5, In step S2, the ultrasonic time is 20 min-40 min.
  2. 2. The method for preparing the silver chloride/silver-copper iron titanium oxide composite material according to claim 1, wherein the method comprises the following steps: Wherein the ratio of the amount of the substances of the citric acid to the tetrabutyl titanate is 1.2:1.
  3. 3. The method for preparing the silver chloride/silver-copper iron titanium oxide composite material according to claim 1, wherein the method comprises the following steps: wherein the mass ratio of the copper nitrate to the ferric nitrate to the tetrabutyl titanate is 1-2:1-3:2-4.
  4. 4. The method for preparing the silver chloride/silver-copper iron titanium oxide composite material according to claim 1, wherein the method comprises the following steps: Wherein, in step S4, sodium hydroxide is used for adjusting the pH value to 9.0-12.0.
  5. 5. The method for preparing the silver chloride/silver-copper iron titanium oxide composite material according to claim 1, wherein the method comprises the following steps: Wherein, when the solvothermal reaction is carried out in the step S5, the reaction temperature is 140-180 ℃ and the reaction time is 14 h-18 h.
  6. 6. The method for preparing the silver chloride/silver-copper iron titanium oxide composite material according to claim 1, wherein the method comprises the following steps: Wherein the mass ratio of the silver nitrate to the sodium chloride is 5:1, and the mass percentage of the silver chloride/silver in the silver chloride/silver-copper iron titanium oxide composite material is 20% -50%.
  7. 7. A silver chloride/silver-copper iron titanium oxide composite material, characterized in that the silver chloride/silver-copper iron titanium oxide composite material is prepared by the preparation method of any one of claims 1-6.
  8. 8. Use of a silver chloride/silver-copper iron titanium oxide composite according to claim 7 for reduction of nitrate by photocatalysis in drinking water treatment.

Description

Silver chloride/silver-copper iron titanium oxide composite material and preparation method and application thereof Technical Field The invention belongs to the technical field of drinking water treatment, and particularly relates to a silver chloride/silver-copper iron titanium oxide composite material, and a preparation method and application thereof. Background Nitrate (NO 3-) is used as a common nonmetallic oxide in water, has high solubility and fluidity, and widely exists in natural water and artificially treated water in the world. Underground water is used as an important drinking water source, the problem of exceeding nitrate in north China and in some areas exists, excessive intake can be converted into nitrite in human bodies, various diseases such as iron red blood protein diseases and the like can be caused, and the health of the human bodies is seriously threatened. Advanced reduction technologies (ARPs) are used as novel water treatment technologies, and active groups generated by activation are utilized to effectively reduce nitrate into ammonium and nitrogen and other substances, wherein the nitrogen conversion rate is improved to make the product harmless. In addition, the heterogeneous photocatalytic treatment technology can reduce the dosage of chemical agents, and the magnetic material also has the advantages of being convenient to recycle and reducing secondary pollution, so that the material and the technology have more practical values. Nitrate has the characteristics of small molecular weight, stable property and the like, and the treatment methods commonly adopted in the drinking water at present are a physical method, a chemical method and a biological method (less biological treatment is adopted in the drinking water treatment technology), such as a reverse osmosis membrane method, an ion exchange method, an adsorption method, a chemical reduction method and an electrochemical reduction method. Compared with the defects of high energy consumption, high chemical agent addition amount, low harsh reaction conditions and removal rate and the like of the methods, the active group-based advanced reduction method has wide prospect as a novel technology in recent years. The research shows that E aq-、H·、CO2·-、SO32- and other reducing free radicals can reduce nitrate effectively under mild condition, and the research shows that CO 2·- can improve nitrogen conversion rate (E DEG (CO 2/CO2·-)＝-2.3eV,E°(NO3-/N2) = -1.25 eV). In-phase advanced reduction requires additional chemical agents, and secondary pollution such as metal ions, organic matters and the like can be caused. In contrast, the heterogeneous advanced reduction technology has the advantages of less additive addition, improved nitrogen conversion rate, effective mineral additive conversion into CO 2, reduced secondary pollution and great application prospect in drinking water treatment. The prior heterogeneous advanced reduction technology is researched to take titanium as an oxide main material, and also related researches of sulfide, spinel, perovskite and the like are carried out, so that the risk of secondary pollution of the catalyst exists. Silver nano particles have surface plasmon resonance effect, and can effectively prolong the service life of photoelectrons and improve the reduction efficiency by using silver modification, but the effect of the silver modified TiO 2 is obviously reduced after the silver modified TiO 2 is recycled, and the recovery is difficult. The copper-iron bimetallic material and the titanium-based oxide material both have good photoelectric effect, and the copper-iron-titanium oxide catalyst has the characteristics of wide preparation materials, simple preparation, stable property, no toxicity and the like, and particularly has magnetism which is convenient for recycling, is a green and efficient catalyst, and has good prospect and fresh research in drinking water treatment. Silver chloride (ecb= -0.13eV and evb= -3.02 eV) is used as a catalytic material, and can form heterojunction with copper-iron-titanium oxide, so that electron and hole recombination is reduced, the photon yield is improved, and the pollutant efficiency and the product nitrogen selectivity are effectively improved. However, at present, systematic research on removal of nitrate pollutants by adopting a copper-iron-titanium mixed metal catalyst and combining a high-grade reduction technology in the field of drinking water treatment has not been reported. Disclosure of Invention The invention aims to solve the problems, and aims to provide a silver chloride/silver-copper iron titanium oxide composite material, and a preparation method and application thereof. The invention provides a preparation method of a silver chloride/silver-copper iron titanium oxide composite material, which has the characteristics that: Step S1, dissolving citric acid in an ethanol solution, stirring and carrying out ultrasonic treatment to obtain a mixed