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CN-121990648-A - Nanotube array membrane electrode, preparation method and application thereof, and electrocatalytic reactor

CN121990648ACN 121990648 ACN121990648 ACN 121990648ACN-121990648-A

Abstract

The invention provides a nanotube array membrane electrode, a preparation method and application thereof, and an electrocatalytic reactor. The nanotube array membrane electrode comprises a titanium substrate, a titanium dioxide nanotube array which grows on the surface of the titanium substrate, and cobalt active species which is loaded on the titanium dioxide nanotube array. The nanotube array membrane electrode has high catalytic activity and good stability, and is suitable for degrading and removing organic pollutants in a continuous flow reaction system.

Inventors

  • WANG XIAOXIONG
  • LIANG YINGHAO

Assignees

  • 清华大学深圳国际研究生院

Dates

Publication Date
20260508
Application Date
20260323

Claims (10)

  1. 1. The nanotube array membrane electrode is characterized by comprising a titanium substrate, a titanium dioxide nanotube array which grows on the surface of the titanium substrate, and cobalt active species which is loaded on the titanium dioxide nanotube array.
  2. 2. The nanotube array membrane electrode of claim 1 wherein divalent cobalt and trivalent cobalt in the cobalt active species coexist.
  3. 3. The preparation method of the nanotube array membrane electrode is characterized by comprising the following steps of: (1) Providing a titanium substrate and pre-treating the titanium substrate; (2) Taking the pretreated titanium substrate as an anode, performing anodic oxidation in a fluorine-containing electrolyte, and taking out, washing and drying a sample after the anodic oxidation is finished, wherein the fluorine-containing electrolyte comprises ethylene glycol, water and NH 4 F, the mass ratio of the ethylene glycol to the water is 5:1-7:1, and the mass concentration of NH 4 F in the fluorine-containing electrolyte is 0.3-0.7 wt%; (3) Calcining the sample obtained in the step (2) in an air atmosphere at 600-650 ℃ to obtain a TiO 2 nanotube array on a titanium substrate; (4) Carrying out reduction reaction on a titanium substrate with a TiO 2 nanotube array formed in a reducing atmosphere at 700-800 ℃ to obtain a titanium dioxide nanotube array on the titanium substrate; (5) Dissolving cobalt salt in absolute ethyl alcohol, wherein the concentration of the cobalt salt is 0.01-0.1g/mL, and obtaining cobalt salt precursor solution; (6) And (3) completely immersing the sample obtained in the step (4) in the cobalt salt precursor solution for a preset time, taking out, drying, and carrying out heat treatment at 300 ℃ in a reducing atmosphere so that cobalt active species are loaded on the titanium dioxide nanotube array.
  4. 4. The preparation method of the titanium alloy material, as set forth in claim 3, wherein the titanium substrate in the step (1) is a titanium sheet, and the pretreatment of the titanium substrate in the step (1) comprises immersing the titanium substrate in a hydrochloric acid solution with a concentration of 1-2 mol/L, treating for 10-20 min under ultrasonic conditions, taking out a sample after the treatment, washing with ultrapure water, sequentially placing the titanium substrate in acetone and absolute ethyl alcohol for ultrasonic cleaning for 10-15 min each time, and drying the cleaned titanium substrate at 80-120 ℃ for later use.
  5. 5. The method according to claim 3, wherein the reducing atmosphere in the step (4) is a mixed gas of hydrogen and nitrogen in a volume ratio of 1:3-1:5, and the total gas flow is 100-120mL/min.
  6. 6. The method according to claim 3, wherein the cobalt salt in the step (5) is Co (NO 3 ) 2 ·6H 2 O), the predetermined time in the step (6) is 20-40min, the reducing atmosphere in the step (6) is H 2 /N 2 mixed gas with the volume fraction of H 2 of 5-10%, and the heat treatment time is 3H.
  7. 7. An electrocatalytic reactor for degrading organic contaminants in a body of water, comprising: A reactor body; The nanotube array membrane electrode of any one of claims 1-2 which is disposed within the reactor body as a working electrode, electrocatalytically activating a peroxymonosulfate to degrade organic contaminants in a body of water.
  8. 8. The electrocatalytic reactor of claim 7, wherein: the electrocatalytic reactor is configured for batch experiments, the electrocatalytic reactor further comprising a counter electrode and a reference electrode, the counter electrode being a platinum sheet, the potential of the working electrode being controlled to be-0.5V to-1.5V relative to the reference electrode; or the electrocatalytic reactor is configured to be used for continuous flow experiments, the reactor body is provided with a water inlet and a water outlet, the electrocatalytic reactor further comprises a ruthenium iridium titanium mesh electrode serving as an anode, a nanotube array membrane electrode serving as a cathode, the anode and the cathode are arranged in the reactor body at intervals of a parallel plate structure, and the electrocatalytic reactor is configured to enable a water body to be treated to enter from the water inlet at a flow of 0.1-0.4 mL/min, sequentially pass through the anode and the cathode and then flow out from the water outlet.
  9. 9. Use of a nanotube array membrane electrode according to any one of claims 1-2 for electrocatalytically activating a peroxymonosulfate to degrade organic pollutants in a body of water.
  10. 10. The use according to claim 9, wherein the concentration of the peroxomonosulphate is 0.25-1 mmol/L in the use and 0.1mol/L Na 2 SO 4 is also added as supporting electrolyte in the use.

Description

Nanotube array membrane electrode, preparation method and application thereof, and electrocatalytic reactor Technical Field The invention relates to an electrochemical water treatment technology, in particular to a nanotube array membrane electrode, a preparation method and application thereof and an electrocatalytic reactor. Background With the development of ocean resources and the increase of offshore engineering activities, domestic sewage and production wastewater generated in the scenes of offshore platforms, ocean vessels, islands and reefs and the like need to be treated on site. Since such areas are typically remote from land-based urban infrastructure, it is difficult to access municipal wastewater treatment systems, while being limited by space conditions, traditional large-scale centralized wastewater treatment processes are difficult to directly apply. Therefore, the development of the miniaturized water treatment technology which has compact structure and stable operation and is suitable for the distributed condition has important significance for marine environment protection and offshore engineering operation. Currently, common water treatment techniques include membrane filtration, biological treatment, chemical oxidation, and the like. The membrane separation technology has the advantages of higher effluent quality, higher equipment cost, easiness in occurrence of membrane pollution, higher requirements on the running environment by the biological treatment technology, poor running stability in space-limited scenes such as offshore platforms and the like, and limited treatment effect on refractory organic pollutants although partial pollutants can be removed by the traditional chemical oxidation method. Therefore, development of a novel water treatment technology capable of efficiently removing hardly degradable organic pollutants is an important direction of current research. In recent years, advanced oxidation techniques based on peroxymonosulfate (Peroxymonosulfate, PMS) activation have been able to generate sulfate radicalsAnd hydroxy radicalsAnd the high-activity oxygen species have good application potential in the aspect of removing refractory organic pollutants. Prior studies have shown that PMS can be activated by transition metals, photoactivation or electrochemical activation. The electrochemical activation PMS system combines the advantages of strong controllability of electrochemical technology, capability of generating various active substances and the like, and can realize high-efficiency oxidative degradation of organic pollutants. However, the existing PMS activation system still has certain defects in practical application. In addition, the traditional homogeneous catalyst is easy to run off in a continuous flow system, is easy to leach out metal ions, affects the catalytic stability and possibly brings secondary pollution risks, is difficult to recover and recycle, and is unfavorable for the long-term stable operation of a distributed water treatment device (such as ocean distributed water treatment scene with limited energy and space conditions). Therefore, the development of the electrode material with high catalytic activity, high stability and controllable structure and the construction of the electrocatalytic PMS activation system suitable for ocean dispersed water treatment scenes are of great significance for improving the organic pollutant removal efficiency and promoting the engineering application of the technology. It should be noted that the information disclosed in the above background section is only for understanding the background of the application and thus may include information that does not form the prior art that is already known to those of ordinary skill in the art. Disclosure of Invention The invention provides a nanotube array membrane electrode, a preparation method and application thereof, and an electrocatalytic reactor, which can realize high-efficiency oxidative degradation of organic pollutants in water. The invention adopts the following technical scheme: in a first aspect, a nanotube array membrane electrode is provided that includes a titanium substrate, a titanium suboxide nanotube array grown on a surface of the titanium substrate, and a cobalt active species supported on the titanium suboxide nanotube array. In a second aspect, a method for preparing a nanotube array membrane electrode is provided, including the steps of: (1) Providing a titanium substrate and pre-treating the titanium substrate; (2) Taking the pretreated titanium substrate as an anode, performing anodic oxidation in a fluorine-containing electrolyte, and taking out, washing and drying a sample after the anodic oxidation is finished, wherein the fluorine-containing electrolyte comprises ethylene glycol, water and NH 4 F, the mass ratio of the ethylene glycol to the water is 5:1-7:1, and the mass concentration of NH 4 F in the fluorine-containing electrolyte is 0.3-0.