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CN-122016969-A - Anti-fouling redox metal electrode based on MOF material modified platinum nano particles, and preparation method and application thereof

CN122016969ACN 122016969 ACN122016969 ACN 122016969ACN-122016969-A

Abstract

The invention provides a platinum nanoparticle antifouling redox metal electrode based on MOF material modification, and a preparation method and application thereof, and belongs to the technical field of marine pollution detection. The invention forms a platinum nano particle substrate by utilizing K 2 PtCl 4 and CTAB electrodeposition on a platinum-based electrode, then utilizes hydrothermal reaction to mix BDC-F 4 and ZrO (NO 3 ) 2 ∙2H 2 O to form UiO-66-F 4 MOF material, and finally puts the electrode into solution to obtain Pt NPs@UiO-66-F 4 .

Inventors

  • PAN YIWEN
  • LU YUANKAI
  • ZHAO DAN

Assignees

  • 浙江大学

Dates

Publication Date
20260512
Application Date
20260324

Claims (10)

  1. 1. The preparation method of the anti-fouling redox metal electrode based on the MOF material modified platinum nano particles is characterized by comprising the following steps of: s1, polishing pretreatment is carried out on a platinum-based electrode, the platinum-based electrode is soaked in sulfuric acid and hydrogen peroxide mixed solution, and the platinum-based electrode is taken out, washed and dried and sleeved with a heat shrinkage tube for packaging; S2, dissolving K 2 PtCl 4 and CTAB in a dilute sulfuric acid solution, and stirring to prepare electroplating solution; s3, placing the platinum-based electrode obtained in the S1 into the electroplating solution obtained in the S2, and electroplating the platinum nano-particles on the platinum-based electrode by using a chronocoulometry at room temperature to obtain an electrode with a platinum nano-particle substrate; And S4, dissolving BDC-F 4 and ZrO (NO 3 ) 2 ∙2H 2 O) in an acetic acid solution, heating in a water bath and stirring to enable the MOF material to complete self-assembly in the solution, and then placing the electrode obtained in the S3 into the solution to enable the generated MOF material to be loaded on the surface of the platinum nano-particles, so as to obtain the anti-fouling redox metal electrode based on the modified platinum nano-particles.
  2. 2. The method according to claim 1, wherein in step S1, the platinum-based electrode is a platinum wire or a composite electrode formed by welding a platinum wire and a gold wire.
  3. 3. The preparation method according to claim 1, wherein in the step S1, the polishing pretreatment of the platinum-based electrode is performed by polishing the platinum-based electrode with aluminum oxide polishing powder with a radius of 1.5-0.05 μm, and then washing the surface with deionized water, wiping or drying.
  4. 4. The preparation method according to claim 1, wherein in the step S1, the formulation of the mixed solution is 98% concentrated sulfuric acid and 30% hydrogen peroxide by weight are mixed in a volume ratio of 3:1, and the soaking time of the electrode in the mixed solution is 20 to 40 minutes.
  5. 5. The method according to claim 1, wherein the concentration of K 2 PtCl 4 in the plating solution in the step S2 is 0.5 to 1 mmol/L, the concentration of CTAB is 0.05 to 0.4 g/L, the concentration of sulfuric acid is 0.25 to 1 mol/L, and the stirring speed in the step S2 is 200 to 500 rpm.
  6. 6. The method for preparing the electrode according to claim 1, wherein the step S3 is characterized in that the platinum-based electrode obtained in the step S1 is used as a working electrode to be plated, the working electrode, a platinum counter electrode and a silver/silver chloride reference electrode are placed into the electroplating solution obtained in the step S2, electroplating is performed at room temperature by using a chronocoulometry, the electroplating parameters are that the maximum voltage is 0-0.2V, the minimum voltage is-0.3-0.1V, the voltage is transited between the maximum voltage and the minimum voltage in the electroplating process, the periodical mutation occurs and the change frequency is 0.1-0.4 Hz, and the electroplating time is 100-400S.
  7. 7. The preparation method according to claim 1, wherein in the solution of step S4, the concentration of BDC-F 4 is 0.05 to 0.2 mol/L, the concentration of ZrO (NO 3 ) 2 ∙2H 2 O is 0.05 to 0.2 mol/L, and the concentration of acetic acid is 5 to 10 mol/L; The solution preparation method in the step S4 comprises the steps of dissolving BDC-F 4 and ZrO (NO 3 ) 2 ∙2H 2 O) in acetic acid solution respectively, heating in a water bath at 40-60 ℃ for 3-10 minutes, mixing the two solutions, and continuing heating at 100-300 rpm for 1-5 minutes.
  8. 8. The preparation method of the electrode according to claim 1, wherein in the step S4, the electrode obtained in the step S3 is put into the solution, specifically, after the electrode is put into the solution, stirring is continued for 1-5 minutes, then stirring is stopped, the electrode is kept stand in the solution for 5-20 minutes, and the temperature of the water bath is kept unchanged during the standing process.
  9. 9. A MOF material modified platinum nanoparticle-based antifouling redox metal electrode prepared according to the method of any one of claims 1 to 8.
  10. 10. The use of the antifouling redox metal electrode of claim 9 as a redox solid state electrode for in situ detection of redox potential in a body of water.

Description

Anti-fouling redox metal electrode based on MOF material modified platinum nano particles, and preparation method and application thereof Technical Field The invention belongs to the technical field of marine water detection, and particularly relates to a platinum nanoparticle antifouling redox metal electrode based on MOF material modification, and a preparation method and application thereof. Background Redox conditions are one of the main determinants and indicators affecting the chemical processes in natural water and sediment. The redox environment in a body of water determines the valence state of the species present, such as the form of iron and manganese, which is primarily regulated by redox conditions, in which they can change from a soluble form to a solid form and in which they dissolve back into the body of water again. The research on the ocean redox conditions can not only know the evolution of the ocean ecosystem and succession of biological communities, but also help to find out shortage resources such as high-quality source rocks, sedimentary manganese carbonate minerals and the like. Therefore, research on redox conditions is carried out, and the method has important significance for finding out the evolution environment of organisms and analyzing the space-time distribution of basin-deposited ore deposits. Currently, an oxidation-reduction potential method with inert metal as a working electrode and a saturated calomel electrode as a reference electrode is mainly used for evaluating oxidation-reduction conditions in water bodies such as seawater. Platinum is widely used for redox potential measurement, and the response mainly depends on the characteristics of the platinum metal surface, especially a thin layer formed on the platinum surface, but platinum is easily affected by biofouling in a solution with high biological content to the response of an electrode, so that a series of problems such as potential drift, slow response time and the like are caused. Therefore, effective solution to the biofouling problem is a key to improving the stability of redox electrodes. Disclosure of Invention Based on the problems, the invention develops a platinum nanoparticle antifouling redox metal electrode based on MOF material modification, and a preparation method and application thereof. According to a first aspect of the invention, the invention provides a preparation method of a platinum nanoparticle antifouling redox metal electrode based on MOF material modification, which comprises the following steps: s1, polishing pretreatment is carried out on a platinum-based electrode, the platinum-based electrode is soaked in sulfuric acid and hydrogen peroxide mixed solution, and the platinum-based electrode is taken out, washed and dried and sleeved with a heat shrinkage tube for packaging; S2, dissolving K 2PtCl4 and CTAB in a dilute sulfuric acid solution, and stirring to prepare electroplating solution; s3, placing the platinum-based electrode obtained in the S1 into the electroplating solution obtained in the S2, and electroplating the platinum nano-particles on the platinum-based electrode by using a chronocoulometry at room temperature to obtain an electrode with a platinum nano-particle substrate; And S4, dissolving BDC-F 4 and ZrO (NO 3)2∙2H2 O) in an acetic acid solution, heating in a water bath and stirring to enable the MOF material to complete self-assembly in the solution, and then placing the electrode obtained in the S3 into the solution to enable the generated MOF material to be loaded on the surface of the platinum nano-particles, so as to obtain the anti-fouling redox metal electrode based on the modified platinum nano-particles. According to some preferred embodiments of the invention, in step S1, the platinum-based electrode is a platinum wire or a composite electrode made by welding a platinum wire and a gold wire. According to some preferred embodiments of the present invention, in step S1, the polishing pretreatment of the platinum-based electrode is performed by polishing the platinum-based electrode with aluminum oxide polishing powder having a radius of 1.5-0.05 μm, and then rinsing the surface with deionized water, wiping or drying. According to some preferred embodiments of the present invention, in step S1, the formulation of the mixed solution is 98% concentrated sulfuric acid and 30% hydrogen peroxide by weight are mixed in a volume ratio of 3:1, and the soaking time of the electrode in the mixed solution is 20 to 40 minutes. According to some preferred embodiments of the present invention, in step S1, the washing process uses deionized water and absolute ethanol. According to some preferred embodiments of the present invention, in the plating solution of step S2, the concentration of K 2PtCl4 is 0.5-1 mmol/L, the concentration of CTAB is 0.05-0.4 g/L, and the concentration of sulfuric acid is 0.25-1 mol/L. Preferably, the stirring speed in S2 is 200-500 rpm. According t