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CN-117800454-B - Palladium/ruthenium/two-dimensional single-layer titanium carbide microphone nano-sheet/three-dimensional foam nickel composite electrode, preparation method and application thereof

CN117800454BCN 117800454 BCN117800454 BCN 117800454BCN-117800454-B

Abstract

The invention discloses a palladium/ruthenium/two-dimensional single-layer titanium carbide microphone nanosheet/three-dimensional foam nickel composite electrode, a preparation method and application thereof, belongs to the technical field of electrochemical materials, and aims to solve the problems that electrode materials with high degradation rate, high efficiency and economy are lacking in the prior art, and development of electrocatalytic degradation antibiotics is limited. The palladium/ruthenium/two-dimensional single-layer titanium carbide microphone nanosheet/three-dimensional foam nickel composite electrode sequentially comprises a foam nickel substrate, a two-dimensional single-layer titanium carbide microphone nanosheet middle layer, a ruthenium middle layer and a palladium layer from inside to outside. The palladium/ruthenium/two-dimensional single-layer titanium carbide microphone nano-sheet/three-dimensional foam nickel composite electrode is used as a working electrode, and the tetracycline wastewater containing electrolyte is degraded by an electrochemical oxidation method. Can efficiently degrade the tetracycline in the wastewater, and does not cause secondary pollution to the water body, thereby achieving the purposes of protecting the environment and saving water resources with low cost.

Inventors

  • ZHANG JIAN
  • LU MUCHEN
  • ZHANG LANHE
  • LI RUOYI
  • WANG BING
  • CHEN ZICHENG

Assignees

  • 东北电力大学

Dates

Publication Date
20260505
Application Date
20240205

Claims (7)

  1. 1. The application of the palladium/ruthenium/two-dimensional single-layer titanium carbide microphone nano-sheet/three-dimensional foam nickel composite electrode is characterized in that the palladium/ruthenium/two-dimensional single-layer titanium carbide microphone nano-sheet/three-dimensional foam nickel composite electrode is used as a working electrode, and tetracycline wastewater containing electrolyte is degraded by an electrochemical oxidation method; The composite electrode sequentially comprises a foam nickel matrix, a two-dimensional single-layer titanium carbide microphone nano-sheet middle layer, a ruthenium middle layer and a palladium layer from inside to outside; the electrode is prepared according to the following method: 1. Preparing a two-dimensional single-layer titanium carbide microphone nano-sheet, namely, preparing titanium carbide microphone by taking MAX-phase titanium carbide aluminum powder as a raw material and adopting an etching method, namely, slowly adding the titanium carbide aluminum powder into etching liquid for multiple times, stirring, then repeatedly cleaning precipitate by deionized water, centrifuging, and finally, adding the precipitate into the deionized water, carrying out ice bath ultrasonic treatment on the precipitate, and obtaining an upper solution to obtain a two-dimensional single-layer titanium carbide microphone nano-sheet dispersion liquid, wherein the etching liquid is a lithium fluoride/hydrochloric acid mixture; 2. Preparing a deposited carbon material intermediate layer, namely sequentially carrying out ultrasonic pretreatment on foam nickel by using hydrochloric acid solution, ethanol and deionized water to remove a surface oxide layer, and drying in a vacuum oven; 3. preparing a deposited ruthenium intermediate layer by adopting a constant current deposition method, taking a two-dimensional single-layer titanium carbide microphone nano-sheet/three-dimensional foam nickel composite electrode as a cathode, taking a platinum sheet as an anode, placing the cathode in parallel with the anode, and taking a sodium sulfate/ruthenium chloride mixed solution as an electrodeposition solution to perform electrodeposition so as to obtain the ruthenium/two-dimensional single-layer titanium carbide microphone nano-sheet/three-dimensional foam nickel composite electrode; 4. and preparing a deposited palladium layer, namely adopting a constant current deposition method to take a ruthenium/two-dimensional single-layer titanium carbide microphone nano-sheet/three-dimensional foam nickel composite electrode as a cathode, taking a platinum sheet as an anode, placing the cathode in parallel with the anode, and taking a sodium sulfate/palladium chloride mixed solution as an electrodeposition solution to carry out electrodeposition so as to obtain the palladium/ruthenium/two-dimensional single-layer titanium carbide microphone nano-sheet/three-dimensional foam nickel composite electrode.
  2. 2. The application of the electrochemical oxidation method for degrading the electrolyte-containing tetracycline wastewater is characterized in that a palladium/ruthenium/two-dimensional single-layer titanium carbide microphone nano-sheet/three-dimensional foam nickel composite electrode is used as a cathode, a platinum sheet is used as an anode, the electrolyte-containing tetracycline aqueous solution is electrolyzed under the condition that the current density is 1mA/cm 2 ~6mA/cm 2 , and the concentration of sodium chloride electrolyte in the tetracycline aqueous solution is 0.3mol/L to 0.5mol/L.
  3. 3. The use according to claim 2, wherein the two-dimensional titanium carbide microphone in the composite electrode has a loading of 1-5 mg/cm 2 , a ruthenium loading of 0.01-0.1 mg/cm 2 and a palladium loading of 0.10-0.20 mg/cm 2 .
  4. 4. The use according to claim 3, wherein in the first step, the etching solution is formed by mixing 1-5 parts by mass of LiF and 40 parts by mass of HCl solution with a concentration of 5-9 mol/L.
  5. 5. The use according to claim 4, wherein the concentration of the monolayer microphone nanoplatelet dispersion in step two is 1-15 mg/mL.
  6. 6. The application of the method according to claim 5, wherein in the third step, the distance between the cathode and the anode is 10 mm-40 mm, the electrodeposition is carried out for 10 min-30 min under the current of 1 mA-10 mA, and the sodium sulfate/ruthenium chloride mixed solution is formed by mixing sodium sulfate solution with the concentration of 0.1-1 mol/L and ruthenium chloride solution with the concentration of 0.01-0.1 mmol/L in equal volumes.
  7. 7. The application of the method according to claim 6, wherein in the fourth step, the distance between the cathode and the anode is 10 mm-40 mm, the electric deposition is carried out for 10 min-30 min under the current of 1 mA-10 mA, and the sodium sulfate/palladium chloride mixed solution is formed by mixing sodium sulfate solution with the concentration of 0.1-1 mol/L and palladium chloride solution with the concentration of 0.01-0.1 mmol/L in equal volumes.

Description

Palladium/ruthenium/two-dimensional single-layer titanium carbide microphone nano-sheet/three-dimensional foam nickel composite electrode, preparation method and application thereof Technical Field The invention belongs to the technical field of electrochemical materials, and particularly relates to a palladium/ruthenium/two-dimensional single-layer titanium carbide microphone nanosheet/three-dimensional foam nickel composite electrode, a preparation method and application thereof. Background Antibiotics have been widely used in human production and life for decades, and tetracycline is a broad-spectrum antibiotic that has been detected in many rivers, soil and other natural environments due to its abuse and mass release in practical use. As only a small part of tetracycline can act in organisms in the medical treatment and the cultivation process, about 1/3~3/4 of tetracycline is discharged into the environment through urine and feces of people or animals, and the tetracycline antibiotics are acid-base amphoteric substances and have stable hydrochloride properties, the tetracycline antibiotics can be degraded in the environment for a long time, once entering the environment, the tetracycline antibiotics can cause serious influence, and certain threats are caused to the ecosystem, public health and safety. Therefore, effective elimination of tetracycline from the water circulation is necessary. In the prior art, the patent with the application number 201811559130.3 provides a method for degrading tetracycline in water, but the method needs to additionally add peroxide into wastewater, so that the method has certain danger and increases the cost, and is not beneficial to popularization and use. In all advanced oxidation, the electrocatalytic oxidation method has the advantages of high efficiency for removing the difficult-to-degrade pollutants, good controllability, no secondary pollution and the like, and is attracting more and more attention. The electrode material plays a crucial role in degradation performance as a main influencing factor in the electrocatalytic process, and the lack of the electrode material with high degradation rate, high efficiency and economy in the prior art limits the development of electrocatalytic degradation antibiotics. Disclosure of Invention The invention aims to solve the technical problems that: The lack of electrode materials with high degradation rate, high efficiency and economy in the prior art limits the development of electrocatalytic degradation of antibiotics. The invention adopts the technical scheme for solving the technical problems: The invention provides a palladium/ruthenium/two-dimensional single-layer titanium carbide microphone nanosheet/three-dimensional foam nickel composite electrode which sequentially comprises a foam nickel substrate, a two-dimensional single-layer titanium carbide microphone nanosheet middle layer, a ruthenium middle layer and a palladium layer from inside to outside. Further, the titanium carbide microphone nano-sheet has a single-layer structure. Further, the two-dimensional titanium carbide microphone in the composite electrode has a load of 1-5 mg/cm 2, ruthenium has a load of 0.01-0.1 mg/cm 2, and palladium has a load of 0.10-0.20 mg/cm 2 Further, the method comprises the following steps: 1. Preparing a two-dimensional single-layer titanium carbide microphone nano-sheet, namely, preparing titanium carbide microphone by taking MAX-phase titanium carbide aluminum powder as a raw material and adopting an etching method, namely, slowly adding the titanium carbide aluminum powder into etching liquid for multiple times, stirring, then repeatedly cleaning precipitate by deionized water, centrifuging, and finally, adding the precipitate into the deionized water, carrying out ice bath ultrasonic treatment on the precipitate, and obtaining an upper solution to obtain a two-dimensional single-layer titanium carbide microphone nano-sheet dispersion liquid, wherein the etching liquid is a lithium fluoride/hydrochloric acid mixture; 2. Preparing a deposited carbon material intermediate layer, namely sequentially carrying out ultrasonic pretreatment on foam nickel by using hydrochloric acid solution, ethanol and deionized water to remove a surface oxide layer, and drying in a vacuum oven; 3. preparing a deposited ruthenium intermediate layer by adopting a constant current deposition method, taking a two-dimensional single-layer titanium carbide microphone nano-sheet/three-dimensional foam nickel composite electrode as a cathode, taking a platinum sheet as an anode, placing the cathode in parallel with the anode, and taking a sodium sulfate/ruthenium chloride mixed solution as an electrodeposition solution to perform electrodeposition so as to obtain the ruthenium/two-dimensional single-layer titanium carbide microphone nano-sheet/three-dimensional foam nickel composite electrode; 4. and preparing a deposited palladium layer, namely adopting a