Preparing method for titanium-based titanium sub-oxide electrode

Abstract

The invention belongs to the technical field of electrochemical oxidation wastewater degradation, and particularly relates to a preparing method for a titanium-based titanium sub-oxide electrode. The preparing method comprises the steps of pretreatment of a titanium substrate, transferred arc cleaning, titanium sub-oxide spraying and surface oxide electrode sintering; titanium servers as a substrate, the titanium substrate is sprayed with titanium sub-oxide powder with the plasma spraying technology, and the titanium-based titanium sub-oxide coating electrode is obtained; part of titanium sub-oxide is formed through oxidation of the titanium substrate at a high temperature, and the conductivity of an electrode material is ensured; a wide electrochemical window is adopted, active sites formed by adding a binding agent on the surface of the electrode are decreased to the maximum degree, the oxygen evolution potential is increased, and background current is reduced; furthermore, use technological parameters of the titanium sub-oxide electrode are determined according to use data obtained in tests, and thus titanium sub-oxide becomes the economical and effective electrode which can be used for electrolyzing wastewater for a long term; the preparing method is simple in technology and reliable in principle, the preparing cost is low, the electrolyzing efficiency is high, the electrolyzing effect is good, the service life is long, the application range is wide, and use is environmentally friendly.

Description

Technical field: [0001] The invention belongs to the technical field of electrochemical oxidation and degradation of sewage, and relates to thermal spraying technology of surface engineering, in particular to a preparation method of a titanium-based titanium suboxide electrode and its use process parameters, which are used for the degradation and oxidation treatment of sewage. Background technique: [0002] The new technology of electrolytic sewage treatment has many advantages such as strong processing capacity, small equipment size, and no secondary pollution. It has been widely used to treat wastewater containing organic pollution such as hydrocarbons, alcohols, aldehydes, ethers, and phenols. The main Depending on the oxidation reaction on the surface of the anode, the organic matter is directly oxidized and degraded on the surface of the anode, or the intermediate product with strong oxidative properties is electrolyzed, and the oxidation of the organic matter and the co...

AI Technical Summary

Problems solved by technology

[0002] The new technology of electrolytic sewage treatment has many advantages such as strong processing capacity, small equipment size, and no secondary pollution. It has been widely used to treat wastewater containing organic pollution such as hydrocarbons, alcohols, aldehydes, ethers, and phenols. The main Depending on the oxidation reaction on the surface of the anode, the organic matter is directly oxidized and degraded on the surface of the anode, or the intermediate product with strong oxidative properties is electrolyzed, and the oxidation of the organic matter and the competition reaction of oxygen evolution are carried out on the anode. - The wastewater with more ions is mainly the precipitation of chlorine gas; in the process of electrolytic treatment of organic wastewater, the electrode not only plays the role of transmitting current, but also catalyzes the oxidation and degradation of organic matter. A necessary condition for the catalytic electrode is to have a High oxygen evolution (chlorine evolution) overpotential, so the choice of electrode material directly affects the degradation efficiency of organic matter. The electrode material should have excellent catalytic activity and conductivity, long corrosion resistance stability and electrode life, wide Electrochemical wide mouth, higher current efficiency and lower price, electrode materials in the prior art include metal electrodes, graphite electrodes, platinum electrodes, metal oxide electrodes and boron-doped diamond film electrodes, wherein metal electrodes are in Dissolution is prone to occur during the electrolysis process, which not only consumes metal electrode materials, but also brings new substances into the solution to pollute the solution, and a passivation film will be formed on the metal surface to affect the conductivity and activity of the electrode; the catalytic performance of the inert electrode platinum electrode The activity is not high, and the platinum electrode is prone to pollution and inactivation during the electrolysis process; the graphite electrode itself has poor strength, and the electrode loss is large when the current density is high; the metal oxide electrode is formed on a metal base (such as Ti, Zr, Ta , Nb, etc.) on which a layer of metal oxide film is deposited has the advantages of low loss and stable dimensions during the electrolysis process: a mixed metal oxide coated electrode disclosed in Chinese patent 201520001915.4 and its preparation method and disclosed in 201510646610.3 A Ti / Sb-SnO 2 / Nd-TiO 2 -PbO 2 The preparation of the electrode and the method of degrading active blue 117 involve the preparation methods of several metal oxide anodes. In the complex sewage environment, the oxygen evolution (chlorine evolution) potential is too low, and the stability of the surface chemical composition and properties is not stable. Good, short life, limited application fields, complex modification work and other issues, not suitable for degrading pollutants such as phenol; boron-doped diamond thin film electrodes have excellent mechanical properties, electrical conductivity and wide electrochemical potential Window, high sewage degradation efficiency, capable of degrading difficult-to-degrade pollutants containing phenol, an organic sewage treatment device using boron-doped diamond electrodes disclosed in Chinese patent 201510289210.1, and P-N junction characteristics BDD-TiO disclosed in 200810103518.2 2 Electrode preparation method and Pd / 3DOMTiO disclosed in 201410186591.6 for photoelectric catalytic reduction treatment of organic pollutants 2 The preparation method of / BDD electrode and its application relate to the preparation method of boron-doped diamond film electrode and the corresponding electrolysis device. However, due to the high price of boron-doped diamond film electrode, the high cost of industrial production, and the difficulty in preparing large-scale electrodes, etc. Restrict its industrial scale production and use; Chinese patent 201510422402.5 discloses an electrode material with a titanium oxide intermediate coating, which involves an electrode material with a titanium oxide intermediate coating, using titanium, aluminum and their alloys as electrodes The inner core structure, the surface is coated with titanium oxide (TiO) with excellent electrochemical properties such as low resistivity, high activity, and good electrochemical corrosion resistance. 4 o 7 ), in order to improve the conductivity of the electrode and protect the inner core material, and then prepare a highly active and cheap metal oxide coating on its surface by electroplating or use a thermal decomposition method to prepare a highly active rare metal oxide, which is only used as an intermediate layer In the field of electrolytic metallurgy; Chinese patent 201410230151.6 discloses a titanium oxide conductive ceramic electrode preparation process using in-situ dehydrogenation technology to prepare sintered electrodes, which has the problems of active impurities on the surface and reduced conductivity; Chinese patent 201510716682.0 discloses a Copper metal plate carrier and titanium oxide film involved in the preparation of copper-based titanium oxide electrode plate, the main component of titanium oxide film is Ti 4 o 7 and TiO 2 , where Ti 4 o 7 The content of titanium oxide is not less than 50% of the total mass of the film. During the long-term electrolysis process with high current, the breakdown potential of the copper substrate is low, and it is easy to corrode and fail. Titanium oxide cannot completely cover the electrode surface; Chinese patent 201410166118.1 is disclosed The preparation method of a titanium / titanium oxide / lead composite substrate is to roughen the surface of the titanium plate before electroplating lead, then sinter a layer of titanium oxide, and then use the conductivity of titanium oxide to plate a layer of titanium oxide on its surface. layer metal lead, to obtain a titanium / titanium oxide / lead composite substrate for bipolar lead-acid batteries, mainly used in lead-acid batteries, compatible with the substrate material; due to the preparation method process of the above titanium oxide electrode Complicated, the electrode itself has the disadvantages of low conductivity and reduced overpotential of oxygen evolution reaction

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