CN110272100B - Ti4O7Preparation method of ceramic microfiltration membrane electrode of coating - Google Patents
Ti4O7Preparation method of ceramic microfiltration membrane electrode of coating Download PDFInfo
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- CN110272100B CN110272100B CN201910477152.3A CN201910477152A CN110272100B CN 110272100 B CN110272100 B CN 110272100B CN 201910477152 A CN201910477152 A CN 201910477152A CN 110272100 B CN110272100 B CN 110272100B
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
- C02F1/46104—Devices therefor; Their operating or servicing
- C02F1/46109—Electrodes
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
- C02F1/467—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction
- C02F1/4672—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction by electrooxydation
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
- C02F1/46104—Devices therefor; Their operating or servicing
- C02F1/46109—Electrodes
- C02F2001/46133—Electrodes characterised by the material
- C02F2001/46138—Electrodes comprising a substrate and a coating
- C02F2001/46142—Catalytic coating
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
- C02F1/46104—Devices therefor; Their operating or servicing
- C02F1/46109—Electrodes
- C02F2001/46152—Electrodes characterised by the shape or form
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/308—Dyes; Colorants; Fluorescent agents
Abstract
The invention relates to Ti4O7The preparation method of the ceramic microfiltration membrane electrode comprises the following steps: preparing polyvinyl alcohol solution, adding titanium dioxide, polyacrylic acid, glycerol and polyvinyl pyrrolidone, and mechanically stirring to form Ti4O7Precursor sol; soaking a flat plate ceramic micro-filtration membrane in a step of coating Ti4O7Dipping the precursor sol into the surface of a flat ceramic microfiltration membrane by lifting and coating Ti4O7Drying the precursor sol film in air to form Ti4O7A ceramic microfiltration membrane electrode coated with precursor gel; the method has the advantages of obtaining Ti4O7Putting the precursor gel coated ceramic microfiltration membrane electrode in a muffle furnace for annealing, and cooling to form Ti4O7A ceramic microfiltration membrane electrode of the precursor coating; step four, synthesizing Ti4O7Annealing and reducing the ceramic microfiltration membrane electrode of the precursor coating in the atmosphere of hydrogen to finally form Ti4O7The ceramic microfiltration membrane electrode of the coating.
Description
Technical Field
The invention relates to the field of electrocatalysis advanced oxidation, in particular to Ti for oxidative degradation of refractory organic wastewater4O7A method for preparing a ceramic microfiltration membrane electrode of a coating.
Background
With the rapid development of the industry in China, the population of cities and towns is continuously expanded, and a large amount of organic wastewater difficult to degrade is generated in the processes of economic production and daily life. The organic wastewater difficult to degrade generally has the characteristics of low biodegradability, complex water quality, high toxicity and the like, and cannot be thoroughly treated by the traditional treatment method. In recent years, annual output of refractory organic wastewater in large and medium-sized cities is on the trend of increasing year by year, and a solution to the problem is a problem which puzzles governments all over the world. The advanced oxidation technology has the advantages of high reaction speed, relatively simple process, good treatment effect and the like, and has good prospect in the aspect of advanced treatment of the organic wastewater difficult to degrade. Electrocatalytic oxidation is one of the advanced oxidation technologies, which produces hydroxyl radicals or oxidants directly or indirectly through electrocatalytic processes to perform oxidative degradation on organic matter. The electrocatalytic oxidation technology has the advantages of simple operation, high efficiency of degrading and mineralizing organic matters, mild operating conditions, less secondary pollutants, strong reaction controllability and the like, and is considered to be the most promising technology for treating the organic wastewater difficult to degrade.
The electrode material is the core of electrocatalytic oxidation. Anodes commonly used in electrocatalytic oxidation processes in recent years mainly include metal oxide electrodes, Dimensionally Stable (DSA) electrodes, and boron-doped diamond (BDD) electrodes. The metal oxide electrode has the advantages of wider potential window, high stability, low cost and the like. Studies have shown that in SnO2And PbO2Hydroxyl radicals can be generated on both electrode surfaces. However, pure SnO2And PbO2The conductivity of the metal oxide is poor, and the conductivity of the metal oxide needs to be improved by doping, but the service life of the doped electrode is greatly shortened. In addition, Sn and Pb have toxicity, and certain Pb can be generated in the electrolytic process2+And Sn2+The ions permeate into the wastewater, causing secondary pollution of the water body. The DSA electrode is a Ti-based electrode with a catalyst coating, and as Ti has strong conductivity and stability, the DSA electrode is superior to metal oxide and graphite electrodes in corrosion resistance and electrode life, and in addition, the cost of Ti is far lower than that of rare metal Pt, the DSA electrode has good application prospect. Compared with a metal oxide electrode, the DSA electrode overcomes the defects of pollution and the like caused by the self dissolution of metal to electrolyte, but a passivation layer is easily formed between the DSA electrode Ti and a coating film, the conductive activity of the electrode is inhibited, and the catalyst layer is easily broken and damaged under the conditions of corrosive solution and gas evolution, so that the service life of the electrode is influenced. The BDD electrode is an anode with optimal performance in the current electrocatalytic oxidation system, and boron is doped in the diamond crystal to enable the diamond crystal to have certain conductivity. Hybridization of carbon atoms in BDD electrode to SP3The hybrid electron cloud structure is more stable, so that the electron cloud structure has higher oxygen evolution potential. In addition, the BDD electrode also has strong corrosion resistance and good chemical stability, and has strong physical adsorption effect on hydroxyl free radicals, so that the BDD electrode has higher reaction activity on oxidative degradation mineralization of organic pollutants. However, the BDD electrode still has limitations, and various researchers have observed that a polymer film is formed on the surface of the BDD electrode, so that passivation of the electrode occurs, and finally electrochemical oxidation sites are causedThe physical efficiency is reduced and the service life of the electrode is reduced. The BDD electrode has higher internal resistance, which causes serious heating in the electrolytic process, reduces the current efficiency and shortens the service life. Furthermore the high cost of BDD electrodes limits their large scale application in practical engineering. In recent years, titanium suboxide electrodes have been considered to be the most promising anode materials for electrocatalytic oxidation systems due to their high electrical conductivity, strong corrosion resistance, high oxygen evolution potential and relatively low cost. Titanium suboxide materials are a general term for a series of non-stoichiometric titanium oxides of the general formula TinO2n-1(n is more than or equal to 4 and less than or equal to 10). Of all the titanium suboxide materials, the Magnesli phase titanium suboxide Ti4O7Is the highest (1500s/cm), three times as high as graphite, and has been registered as Ebonex by foreign companies@And (4) a trademark. Ti4O7Based on rutile TiO2Every 4 layers of rutile structural units, a common oxygen atom shear plane appears. Ti4O7Compared with metal titanium, the metal titanium has excellent corrosion resistance, and does not react with sulfuric acid, nitric acid, hydrochloric acid and caustic soda at normal temperature. Further, Ti4O7The electrochemical property of the catalyst is very stable, the oxygen evolution potential of the catalyst can reach 2.5Vvs. SHE, and the catalyst proves to have good electrolytic catalysis effect on refractory organic wastewater.
Disclosure of Invention
The technical problem solved by the invention is to overcome the defects of high electrode cost and poor effect in the current electrocatalytic oxidation process and provide a method for controlling Ti4O7The annealing temperature and the annealing time of the ceramic microfiltration membrane electrode of the coating in the annealing reduction process are adopted, so that pure-phase Ti is prepared4O7The ceramic microfiltration membrane electrode of the coating. The invention solves another technical problem of providing the Ti with simple method, low cost, stable electrolysis effect, wide potential window, high efficiency of electrolysis catalysis on refractory organics and long service life4O7A method for preparing a ceramic microfiltration membrane electrode of a coating.
The technical solution of the invention is that the Ti is4O7Method for preparing ceramic-coated microfiltration membrane electrodeThe method is characterized by comprising the following steps:
preparing polyvinyl alcohol (PVA) solution, and sequentially adding titanium dioxide (TiO)2) Polyacrylic acid (PAA), glycerol and polyvinylpyrrolidone (PVP), followed by mechanical stirring to form Ti4O7Precursor sol;
soaking the flat-plate ceramic micro-filtration membrane into the Ti obtained in the step4O7In the precursor sol, a layer of Ti is coated on the surface of a flat ceramic microfiltration membrane by lifting and dipping4O7Precursor sol film, then drying in air to form Ti4O7A ceramic microfiltration membrane electrode coated with precursor gel;
the Ti obtained in the step II4O7Placing the precursor gel coated ceramic microfiltration membrane electrode in a muffle furnace for annealing and forming, and cooling to form Ti4O7A ceramic microfiltration membrane electrode of the precursor coating;
step four, synthesizing Ti4O7Annealing and reducing the ceramic microfiltration membrane electrode of the precursor coating in the atmosphere of hydrogen to finally form Ti4O7The ceramic microfiltration membrane electrode of the coating.
Preferably, the method comprises the following steps: titanium dioxide (TiO) of the present invention2) The average particle diameter of (B) is 0.5 to 2 μm.
Preferably, the method comprises the following steps: step (c) the Ti4O7The concentration of PVA in the precursor sol solution is 30-200 mg/L, and TiO2The concentration of the PVP is 100-200 mg/L, the concentration of the PAA is 1-3 mg/L, the concentration of the glycerol is 1-2 mg/L, and the concentration of the PVP is 1-1.5 mg/L.
Preferably, the method comprises the following steps: to increase Ti4O7The viscosity and the film forming stability of the precursor sol are realized, and the concentration of PVA in the sol is 100 mg/L; to increase Ti4O7Stability of precursor coating and Ti4O7Precursor content, TiO in the sol2The concentration was 200 mg/L.
Preferably, the method comprises the following steps: the method comprises the steps of enabling the concentration of PAA in the sol to be 1-3 mg/L, the concentration of glycerol to be 1-2 mg/L and the concentration of PVP to be 1.5 mg/L.
Preferably, the method comprises the following steps: step two, the flat ceramic microfiltration membrane is immersed in Ti4O7The time of the precursor sol is 16-36 s, and the pulling rate is 5-20 cm/s.
Preferably, the method comprises the following steps: step four of4O7The annealing temperature required by the formation of the ceramic microfiltration membrane electrode of the precursor coating is 800-1000 ℃, and the annealing time is 2-4 h.
Preferably, the method comprises the following steps: step four of4O7The annealing temperature of the ceramic microfiltration membrane electrode of the precursor coating in the annealing reduction process is 900-1050 ℃, the annealing time is 2-4 h, and the flow of hydrogen is 40-120 ml/min.
Preferably, the method comprises the following steps: step three, the Ti4O7The annealing temperature of the ceramic microfiltration membrane electrode coated with the precursor gel is 800-1000 ℃, and the annealing time is 2-4 h.
Compared with the prior art, the invention has the beneficial effects that:
first embodiment of the invention4O7The coating crystal composition, the oxygen evolution potential measurement and the surface morphology analysis of the ceramic microfiltration membrane electrode of the coating are as follows:
the resulting pure phase Ti was tested using an X-ray diffractometer (Ultima IV, Rigaku Co. Ltd., Japan)4O7The crystal composition of the coating of the coated ceramic microfiltration membrane electrode was found to be phase pure Ti4O7(ii) a Ti was tested using an electrochemical workstation (CHI760D, Chenhua Instrument Co. Ltd., Shanghai, China)4O7Determining the oxygen evolution potential of the electrode by the polarization curve of the ceramic microfiltration membrane electrode of the coating, wherein the scanning range is 1-3V vs. SHE, the scanning speed is 5mV/s, and Ti is found4O7The oxygen evolution potential of the coated ceramic microfiltration membrane electrode is as high as 2.20Vvs.SHE, which is higher than 1.84Vvs.SHE of a Pt electrode; analysis of Ti by scanning Electron microscopy (Mira3, Tescan, Czech Reublic)4O7The surface morphology of the coated ceramic microfiltration membrane electrode shows that Ti4O7The particles are partially melted to form a net structure, and a large number of pores are generated, and the pore diameters of the pores are intensively distributed in the range of 1-2 mu m.
The invention also discloses Ti4O7The effect analysis of the ceramic microfiltration membrane electrode coated on the refractory organic matters in the electrocatalysis advanced oxidation process:
with Pt electrode and Ti, respectively4O7The ceramic microfiltration membrane electrode of the coating is used as an anode to carry out an experiment for preparing water by electrocatalytic oxidation degradation of azo dye orange yellow II, and the experiment is carried out at a constant current density (20 mA/cm)2) Was carried out under the conditions of (1) and the concentration of orange II in the water was determined by means of a UV spectrophotometer (UV-2450, Shimadzu, Kyoto, Japan). It is found that with Ti4O7The coated ceramic microfiltration membrane electrode can reduce the concentration of orange II in the solution from 21.51mg/L to below 1mg/L in the 1h degradation process of an electrocatalytic oxidation system taking a Pt electrode as an anode, and the concentration of orange II in the solution can be reduced from 21.51mg/L to 13.368mg/L in the 2.5h degradation process of the electrocatalytic oxidation system taking the Pt electrode as the anode. Research proves that Ti4O7The ceramic microfiltration membrane electrode of the coating has extremely strong electrocatalytic degradation effect on refractory organics.
The invention of Ti4O7The annealing temperature and the annealing time of the ceramic microfiltration membrane electrode of the coating in the annealing reduction process are adopted to prepare pure-phase Ti4O7The ceramic microfiltration membrane electrode of the coating. The electrode has the advantages of simple manufacturing method, low cost, stable electrolysis effect, wide potential window, high electrolysis catalysis efficiency on refractory organic matters and long service life.
The invention improves Ti4O7Viscosity of precursor sol, stability of film formation and Ti4O7Stability of precursor coating and Ti4O7Precursor content, reduction of Ti4O7The water content of the precursor gel film and the generation rate of cracks in the annealing forming process are inhibited.
Drawings
FIG. 1 is a view of Ti of the present invention4O7A precursor sol object diagram;
FIG. 2 is a view of Ti of the present invention4O7A coated ceramic microfiltration membrane electrode object graph;
FIG. 3 isTi of the invention4O7The X-ray diffraction pattern of the ceramic microfiltration membrane electrode of the coating;
FIG. 4 is a view of Ti of the present invention4O7Polarization curve diagrams of the ceramic microfiltration membrane electrode and the Pt electrode of the coating;
FIG. 5 is a view of Ti of the present invention4O7The scanning electron microscope of the ceramic microfiltration membrane electrode of the coating is like an image;
FIG. 6 is Ti4O7The effect diagram of the water distribution of the ceramic microfiltration membrane electrode and the Pt electrode of the coating for electrocatalysis advanced oxidation degradation of orange II.
Detailed Description
The invention will be further described in detail with reference to the following examples:
Ti4O7the preparation method of the ceramic microfiltration membrane electrode comprises the following steps:
⑴Ti4O7preparing precursor sol:
putting 10g of PVA in a beaker, pouring deionized water to 100ml, then putting the beaker on a heating plate (IKA, RT-10) at 105 ℃ to dissolve the PVA, and adding a proper amount of deionized water in the dissolving process to supplement the evaporation loss of the deionized water; after cooling, 20g of TiO are added in turn22g of PAA, 1.5g of glycerol and 1.2g of PVP are stirred, and finally deionized water is used for fixing the volume to 100 ml; the sol was mechanically stirred with a stirrer (IKA, RW-20) at 900rpm to strengthen the TiO2Dispersing in sol, stirring to obtain Ti4O7Precursor sol;
⑵Ti4O7preparation of a precursor gel-coated ceramic microfiltration membrane:
ti coating by using PTL-OV5P pulling coating machine4O7Preparing a ceramic microfiltration membrane coated with precursor gel, fixing a flat ceramic microfiltration membrane (25mm multiplied by 30mm, and the average pore diameter is 1 mu m) which is cleaned by ultrasonic on a lifting table, and then immersing the flat ceramic microfiltration membrane into Ti4O7Dipping in the precursor sol for 25s, uniformly lifting the flat ceramic microfiltration membrane at a speed of 10cm/s after dipping, and uniformly lifting the flat ceramic microfiltration membrane with Ti4O7The precursor sol is separated and then 25Naturally drying at the temperature of 18 ℃ and the relative humidity of 30% for 18h to form Ti4O7A ceramic microfiltration membrane coated with precursor gel;
⑶Ti4O7annealing and forming the precursor-coated ceramic microfiltration membrane:
drying the Ti4O7Placing the precursor gel-coated ceramic microfiltration membrane in a muffle furnace (KSL-1200X-J), heating to 1000 ℃ at the speed of 5 ℃/min, keeping the temperature for 4 hours, and cooling to room temperature to obtain Ti4O7A ceramic microfiltration membrane of the precursor coating;
⑷Ti4O7annealing and reducing the coated ceramic microfiltration membrane electrode:
will obtain Ti4O7Placing the ceramic microfiltration membrane of the precursor coating in a tube furnace (OTF-1200X-II), taking hydrogen (80mL/min) as carrier gas, heating to 950 ℃ at the speed of 5 ℃/min, keeping the temperature for 2h, and cooling to room temperature to obtain Ti4O7A ceramic microfiltration membrane electrode of the coating;
⑸Ti4O7the coating crystal composition, the oxygen evolution potential measurement and the surface morphology analysis of the ceramic microfiltration membrane electrode of the coating are as follows:
the resulting phase-pure Ti was tested using an X-ray diffractometer (UltimaIV, Rigaku Co. Ltd. Japan)4O7The crystal composition of the coating of the coated ceramic microfiltration membrane electrode was found to be phase pure Ti4O7(ii) a Ti was tested using an electrochemical workstation (CHI760D, Chenhua Instrument Co. Ltd., Shanghai, China)4O7Determining the oxygen evolution potential of the electrode by the polarization curve of the ceramic microfiltration membrane electrode with the coating, wherein the scanning range is 1-3 Vvs.SHE, the scanning speed is 5mV/s, and Ti is found4O7The oxygen evolution potential of the coated ceramic microfiltration membrane electrode is as high as 2.20Vvs.SHE, which is higher than 1.84Vvs.SHE of a Pt electrode; analysis of Ti by scanning Electron microscopy (Mira3, Tescan, Czech Reublic)4O7The surface morphology of the coated ceramic microfiltration membrane electrode shows that Ti4O7The particles are partially melted to form a net structure and generate a large number of pores, and the pore diameters of the pores are intensively distributed in the range of 1-2 mu m;
⑸Ti4O7The effect analysis of the ceramic microfiltration membrane electrode coated on the refractory organic matters in the electrocatalysis advanced oxidation process:
with Pt electrode and Ti, respectively4O7The ceramic microfiltration membrane electrode of the coating is used as an anode to carry out an experiment for preparing water by electrocatalytic oxidation degradation of azo dye orange yellow II, and the experiment is carried out at a constant current density (20 mA/cm)2) Was carried out under the conditions of (1) and the concentration of orange II in the water was determined by means of a UV spectrophotometer (UV-2450, Shimadzu, Kyoto, Japan). It is found that with Ti4O7The coated ceramic microfiltration membrane electrode can reduce the concentration of orange II in the solution from 21.51mg/L to below 1mg/L in the 1h degradation process of an electrocatalytic oxidation system taking a Pt electrode as an anode, and the concentration of orange II in the solution can be reduced from 21.51mg/L to 13.368mg/L in the 2.5h degradation process of the electrocatalytic oxidation system taking the Pt electrode as the anode. Research proves that Ti4O7The ceramic microfiltration membrane electrode of the coating has extremely strong electrocatalytic degradation effect on refractory organics.
The above-mentioned embodiments are only preferred embodiments of the present invention, and all equivalent changes and modifications made within the scope of the claims of the present invention should be covered by the claims of the present invention.
Claims (4)
1. Ti4O7The preparation method of the ceramic microfiltration membrane electrode of the coating is characterized by comprising the following steps:
preparing polyvinyl alcohol (PVA) solution, and sequentially adding titanium dioxide (TiO)2) Polyacrylic acid (PAA), glycerol and polyvinylpyrrolidone (PVP), followed by mechanical stirring to form Ti4O7Precursor sol;
soaking the flat-plate ceramic micro-filtration membrane into the Ti obtained in the step4O7In the precursor sol, a layer of Ti is coated on the surface of a flat ceramic microfiltration membrane by lifting and dipping4O7Precursor sol film, then drying in air to form Ti4O7A ceramic microfiltration membrane electrode coated with precursor gel;
the Ti obtained in the step II4O7Placing the precursor gel coated ceramic microfiltration membrane electrode in a muffle furnace for annealing and forming, and cooling to form Ti4O7A ceramic microfiltration membrane electrode of the precursor coating;
step four, synthesizing Ti4O7Annealing and reducing the ceramic microfiltration membrane electrode of the precursor coating in the atmosphere of hydrogen to finally form Ti4O7A ceramic microfiltration membrane electrode of the coating;
titanium dioxide (TiO) of the present invention2) The average particle diameter of (2) is 0.5 to 2 μm;
step (c) the Ti4O7The concentration of PVA in the precursor sol solution is 30-200 mg/L, and TiO2The concentration of the PVP is 100-200 mg/L, the concentration of PAA is 1-3 mg/L, the concentration of glycerol is 1-2 mg/L, and the concentration of PVP is 1-1.5 mg/L;
step three, the Ti4O7The annealing temperature of the ceramic microfiltration membrane electrode coated with the precursor gel is 800-1000 ℃, and the annealing time is 2-4 h;
step four of4O7The annealing temperature required by the formation of the ceramic microfiltration membrane electrode of the precursor coating is 800-1000 ℃, and the annealing time is 2-4 h.
2. The Ti of claim 14O7The preparation method of the ceramic microfiltration membrane electrode of the coating is characterized in that the preparation method is used for improving Ti4O7The viscosity and the film forming stability of the precursor sol are realized, and the concentration of PVA in the sol is 100 mg/L; to increase Ti4O7Stability of precursor coating and Ti4O7Precursor content, TiO in the sol2The concentration was 200 mg/L.
3. The Ti of claim 14O7The preparation method of the coated ceramic microfiltration membrane electrode is characterized by comprising the step of immersing the flat ceramic microfiltration membrane into Ti4O7The time of the precursor sol is 16-36 s, and the pulling rate is 5-20 cm/s.
4. The Ti of claim 14O7The preparation method of the coated ceramic microfiltration membrane electrode is characterized by comprising the step of preparing the Ti4O7The annealing temperature of the ceramic microfiltration membrane electrode of the precursor coating in the annealing reduction process is 900-1050 ℃, the annealing time is 2-4 h, and the flow of hydrogen is 40-120 ml/min.
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| CN111592078B (en) * | 2020-05-09 | 2022-10-25 | 哈尔滨工业大学 | Device and method for treating chlorophenol wastewater by using ultrasonic-assisted active membrane electrode |
| CN111875002B (en) * | 2020-08-04 | 2022-11-18 | 盐城工学院 | Preparation method of microspheric titanium suboxide electrode |
| CN113213594B (en) * | 2021-05-28 | 2022-04-01 | 东莞理工学院 | Rare earth metal doped Ti4O7Method for preparing electrode |
| CN115947420A (en) * | 2022-06-09 | 2023-04-11 | 松山湖材料实验室 | High-conductivity Magneli-phase titanium suboxide ceramic coating electrode and slurry, preparation method and application thereof |
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