CN111254435A - Ti/Sb-SnO2/PVDF-CNT-PbO2Electrode and method for producing same - Google Patents

Ti/Sb-SnO2/PVDF-CNT-PbO2Electrode and method for producing same Download PDF

Info

Publication number
CN111254435A
CN111254435A CN202010087985.1A CN202010087985A CN111254435A CN 111254435 A CN111254435 A CN 111254435A CN 202010087985 A CN202010087985 A CN 202010087985A CN 111254435 A CN111254435 A CN 111254435A
Authority
CN
China
Prior art keywords
sno
electrode
titanium substrate
pbo
cnt
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN202010087985.1A
Other languages
Chinese (zh)
Inventor
唐玉霖
龙昕
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Tongji University
Original Assignee
Tongji University
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Tongji University filed Critical Tongji University
Priority to CN202010087985.1A priority Critical patent/CN111254435A/en
Publication of CN111254435A publication Critical patent/CN111254435A/en
Pending legal-status Critical Current

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • C23C28/04—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings of inorganic non-metallic material
    • 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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
    • C23C18/04—Pretreatment of the material to be coated
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
    • C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
    • C23C18/1204—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material inorganic material, e.g. non-oxide and non-metallic such as sulfides, nitrides based compounds
    • C23C18/1208—Oxides, e.g. ceramics
    • C23C18/1216—Metal oxides
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
    • C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
    • C23C18/1229—Composition of the substrate
    • C23C18/1241—Metallic substrates
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D15/00—Electrolytic or electrophoretic production of coatings containing embedded materials, e.g. particles, whiskers, wires
    • 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

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Mechanical Engineering (AREA)
  • Electrochemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Hydrology & Water Resources (AREA)
  • Environmental & Geological Engineering (AREA)
  • Water Supply & Treatment (AREA)
  • Ceramic Engineering (AREA)
  • Electrodes For Compound Or Non-Metal Manufacture (AREA)

Abstract

The invention discloses a Ti/Sb-SnO2/PVDF‑CNT‑PbO2An electrode and a preparation method thereof belong to the technical field of electrocatalysis. The preparation method of the electrode comprises the following steps: firstly, carrying out ultrasonic cleaning, alkali washing, ultrasonic cleaning and acid washing pretreatment on a titanium matrix to form uniform pitted surface, then placing the pretreated titanium matrix in a middle layer coating solution for soaking, and then drying and firing to obtain the Sb-SnO deposited2Finally, the Ti matrix of the oxide intermediate layer is electrodeposited in electroplating solution containing carbon nano tubes and polyvinylidene fluoride to obtain Ti/Sb-SnO2/PVDF‑CNT‑PbO2And an electrode. The invention realizes the effect of the carbon nano tube and the polyvinylidene fluoride in PbO by adding the carbon nano tube and the polyvinylidene fluoride into the electroplating solution2Co-doping in the active layer to prepare Ti/Sb-SnO2/PVDF‑CNT‑PbO2Electrodes, and unmodified and singly doped modified Ti/Sb-SnO2/PbO2Electrode phase, Ti/Sb-SnO2/PVDF‑CNT‑PbO2The catalytic activity of the electrode and the service life of the electrode are both improved.

Description

Ti/Sb-SnO2/PVDF-CNT-PbO2Electrode and method for producing same
Technical Field
The invention particularly relates to Ti/Sb-SnO2/PVDF-CNT-PbO2An electrode and a preparation method thereof belong to the technical field of electrocatalysis.
Background
With the rapid development of industries of all countries in the world, the discharge amount of waste water is increased rapidly, and particularly, the waste water discharged by the industries such as chemistry, pesticide, dye, medicine, food and the like has high concentration, large chromaticity and strong toxicity, contains a large amount of components which are difficult to degrade biologically, causes serious pollution to the global water environment, and causes harm to the ecological environment and human health.
The conventional wastewater treatment technology has difficulty in meeting the requirements for treating the wastewater with high concentration and strong toxicity, and the advanced oxidation technology is continuously researched and developed rapidly. Among them, electrocatalytic technology has become a hot spot in the research field of modern advanced oxidation technology. The electrocatalytic oxidation method has the advantages that: only a power supply needs to be provided, electrons participate, and other chemical reagents are not needed, so that secondary pollution caused by addition of a high-grade oxidation reagent is avoided; the reaction condition is mild, the occupied area of equipment is small, and the operation is convenient; can be treated independently or combined with other processes, and has the functions of flocculation, air flotation, disinfection and the like.
The electrode material of the anode is the most important factor affecting the efficiency of the electrocatalytic oxidation. The appearance of the Dimensionally Stable Anode electrode (DSA) overcomes the defects of the traditional electrode, and is an electrocatalytic electrode with excellent performance in the field of electrochemical oxidation. The DSA electrode can keep the stability of the polar plate, so that the cell voltage is kept stable in the electrolysis process, and the stable current required in the electrolysis process is further ensured to be provided; compared with the traditional electrode, the DSA electrode has the advantages of low working voltage, low energy consumption and stronger corrosion resistance in the using process, and can prolong the service life of the electrode, thereby improving the efficiency of organic pollutant treatment. Among various kinds of DSA electrodes, PbO2The electrode has many advantages, and has the advantages of higher oxygen evolution potential, stable chemical property, long service life, low price and the like.
To increase PbO2Electrode active, most conventional PbO2The electrode takes Ti as a substrate and is combined with an Sb-SnO intermediate layer2Obtain higher catalytic activity and stabilityGood Ti/Sb-SnO2/PbO2And an electrode. At present, when a surface active layer is electrodeposited, certain active substances are doped to modify the surface active layer, so that the performance of an electrode is further improved. But currently on Ti/Sb-SnO2/PbO2The active doping of the electrode is mostly the doping of a single active substance, and the doping mode has limited improvement on the performance of the electrode.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides Ti/Sb-SnO2/PVDF-CNT-PbO2The invention realizes the effect of adding the carbon nano tube and the polyvinylidene fluoride in the PbO by adding the carbon nano tube and the polyvinylidene fluoride in the electroplating solution2Co-doping in the active layer to prepare Ti/Sb-SnO2/PVDF-CNT-PbO2Electrodes, and unmodified and singly doped modified Ti/Sb-SnO2/PbO2Electrode phase, Ti/Sb-SnO2/PVDF-CNT-PbO2The catalytic activity of the electrode and the service life of the electrode are both improved.
In order to achieve the technical purpose, the technical scheme of the invention is as follows:
Ti/Sb-SnO2/PVDF-CNT-PbO2The preparation method of the electrode comprises the following steps:
(1) matrix pretreatment: putting a titanium substrate into distilled water, ultrasonically cleaning, soaking the cleaned titanium substrate into a NaOH solution with the mass fraction of 30-50%, carrying out alkali cleaning at 50-80 ℃ for 2h, then soaking the titanium substrate after the alkali cleaning in the distilled water, ultrasonically cleaning, then putting the titanium substrate into an oxalic acid solution with the mass fraction of 10-30%, carrying out acid etching at 80-100 ℃ for 2h to form uniform pitted surface, washing the etched titanium substrate with distilled water, and putting the cleaned titanium substrate into absolute ethyl alcohol for later use;
(2) preparing an intermediate layer: adding 3-10 g SnCl4·5H2O and 0.2 to 0.5g of SbCl3Dissolving in 25mL of isopropanol, and adding 2.5mL of concentrated hydrochloric acid to obtain an intermediate layer coating solution; soaking the titanium substrate pretreated in the step (1) in the intermediate layer coating solution, drying in a drying oven at 150 ℃ for 10min, then putting in a muffle furnace for firing at 500 ℃ for 10min, repeatedly soaking, drying and firing for several times, and finally placing in the muffle furnaceAnnealing at medium 500 ℃ for 1h to obtain Sb-SnO2A titanium substrate of an oxide interlayer;
(3) depositing Sb-SnO obtained in the step (2)2Taking a titanium substrate of the oxide intermediate layer as an anode and graphite with equal area as a cathode, and electrodepositing a surface active layer in electroplating solution to obtain Ti/Sb-SnO2/PVDF-CNT-PbO2An electrode, wherein the plating solution contains Pb (NO)3)2，NaF，HNO3Carbon nano tube and polyvinylidene fluoride, and the electrodeposition conditions are as follows: the current density is 10-80 mA/cm2The temperature is 50-80 ℃, and the electrodeposition time is 0.5-1 h.
Preferably, Pb (NO) as described in step (3)3)2The concentration is 0.5 to 1.0 mol/L.
Preferably, the concentration of NaF in the step (3) is 0.01-0.05 mol/L.
Preferably, HNO described in step (3)3The concentration is 0.5 to 1.0 mol/L.
Preferably, the concentration of the carbon nanotubes in the step (3) is 0-4 g/L.
Preferably, the concentration of the polyvinylidene fluoride in the step (3) is 0-4 g/L.
Preferably, the titanium substrate in the step (1) is TA2 titanium sheet.
Preferably, the number of the repeated operations in the step (2) is 10.
Ti/Sb-SnO prepared by adopting preparation method2/PVDF-CNT-PbO2And an electrode.
From the above description, it can be seen that the present invention has the following advantages:
1. the polyvinylidene fluoride has stable chemical property, is embedded in the coating in the electrodeposition process, fills and seals partial gaps, and can avoid β -PbO2The continuous deposition of the carbon nanotube can disperse the internal stress in the coating, enhance the toughness and mechanical strength of the coating, thereby improving the corrosion resistance of the electrode, and simultaneously, the specific surface area of the CNT can provide a large number of active points for electrochemical reaction. The invention realizes that PVDF and CNT are in PbO by adding the carbon nano tube and the polyvinylidene fluoride into the electroplating solution2Codoping in active layersTo prepare Ti/Sb-SnO2/PVDF-CNT-PbO2Electrodes, and unmodified and singly doped modified Ti/Sb-SnO2/PbO2Electrode phase, Ti/Sb-SnO2/PVDF-CNT-PbO2The catalytic activity of the electrode and the service life of the electrode are both improved.
Drawings
FIG. 1 is a graph showing polarization curves of electrodes prepared in example 1 and comparative examples 1 to 3;
FIG. 2 is a Tafel plot of the electrodes prepared in example 1 and comparative examples 1-3;
FIG. 3 is a graph showing the enhanced life time of the electrodes prepared in example 1 and comparative example 1;
Detailed Description
The features of the invention will be further elucidated by the following examples, without limiting the claims of the invention in any way.
Example 1
Ti/Sb-SnO2/PVDF-CNT-PbO2The preparation method of the electrode comprises the following steps:
(1) matrix pretreatment: putting a titanium substrate (adopting a TA2 titanium sheet, the size of which is 1cm multiplied by 1cm and the thickness of which is 1mm) into distilled water, ultrasonically cleaning for 30min, soaking the cleaned titanium substrate into a NaOH solution with the mass fraction of 40%, alkaline cleaning for 2h at 80 ℃, then soaking the titanium substrate after alkaline cleaning in the distilled water, ultrasonically cleaning for 30min, then placing the titanium substrate into an oxalic acid solution with the mass fraction of 30%, acid etching for 2h at 98 ℃ to form a uniform pitted surface, enhancing the bonding force between the titanium substrate and a metal oxide film layer, completely washing the etched titanium substrate with distilled water, and then placing the titanium substrate into absolute ethyl alcohol for later use;
(2) preparing an intermediate layer: 5g of SnCl4·5H2O and 0.3g of SbCl3Dissolving in 25mL of isopropanol, and adding 2.5mL of concentrated hydrochloric acid to prevent hydrolysis to obtain an intermediate layer coating solution; soaking the titanium substrate pretreated in the step (1) in the intermediate layer coating solution, drying in a drying oven at 150 ℃ for 10min, then placing in a muffle furnace for firing at 500 ℃ for 10min, repeatedly performing soaking-drying-firing for 10 times, and finally annealing in the muffle furnace at 500 ℃ for 1h to obtain the titanium substrateWith Sb-SnO deposited2A titanium substrate of an oxide interlayer;
(3) depositing Sb-SnO obtained in the step (2)2Taking a titanium substrate of the oxide intermediate layer as an anode and graphite with equal area as a cathode, and electrodepositing a surface active layer in 20mL of electroplating solution to obtain Ti/Sb-SnO2/PVDF-CNT-PbO2An electrode, wherein the plating solution contains 0.5mol/L Pb (NO)3)2，0.01mol/L NaF，1.0mol/L HNO 32g/L carbon nano tube and 3g/L polyvinylidene fluoride, and the electrodeposition conditions are as follows: current density 20mA/cm2The temperature is 50 ℃, and the electrodeposition time is 1 h.
Tests show that the Ti/Sb-SnO prepared by the method2/PVDF-CNT-PbO2The oxygen evolution overpotential of the electrode (as shown in FIG. 1) was 1.91V, the Tafel slope (as shown in FIG. 2) was 0.19, and the accelerated lifetime (as shown in FIG. 3) was 12h (actual lifetime was about 2598 days).
Comparative example 1
Ti/Sb-SnO2/PbO2The preparation method of the electrode comprises the following steps:
(1) matrix pretreatment: putting a titanium substrate (adopting a TA2 titanium sheet, the size of which is 1cm multiplied by 1cm and the thickness of which is 1mm) into distilled water, ultrasonically cleaning for 30min, soaking the cleaned titanium substrate into a NaOH solution with the mass fraction of 40%, alkaline cleaning for 2h at 80 ℃, then soaking the titanium substrate after alkaline cleaning in the distilled water, ultrasonically cleaning for 30min, then placing the titanium substrate into an oxalic acid solution with the mass fraction of 30%, acid etching for 2h at 98 ℃ to form a uniform pitted surface, enhancing the bonding force between the titanium substrate and a metal oxide film layer, completely washing the etched titanium substrate with distilled water, and then placing the titanium substrate into absolute ethyl alcohol for later use;
(2) preparing an intermediate layer: 5g of SnCl4·5H2O and 0.3g of SbCl3Dissolving in 25mL of isopropanol, and adding 2.5mL of concentrated hydrochloric acid to prevent hydrolysis to obtain an intermediate layer coating solution; soaking the titanium substrate pretreated in the step (1) in the intermediate layer coating solution, drying in a drying oven at 150 ℃ for 10min, then placing in a muffle furnace for firing at 500 ℃ for 10min, repeatedly performing soaking-drying-firing for 10 times, and finally annealing in the muffle furnace at 500 ℃ for 1h to obtain the coating material deposited with Sb-SnO2A titanium substrate of an oxide interlayer;
(3) depositing Sb-SnO obtained in the step (2)2Taking a titanium substrate of the oxide intermediate layer as an anode and graphite with equal area as a cathode, and electrodepositing a surface active layer in 20mL of electroplating solution to obtain Ti/Sb-SnO2/PbO2An electrode, wherein the plating solution contains 0.5mol/L Pb (NO)3)2，0.01mol/L NaF，1.0mol/L HNO3The electrodeposition conditions were: current density 20mA/cm2The temperature is 50 ℃, and the electrodeposition time is 1 h.
Tests show that the Ti/Sb-SnO prepared by the method2/PbO2The oxygen evolution overpotential of the electrode (as shown in FIG. 1) was 1.80V, the Tafel slope (as shown in FIG. 2) was 0.36, and the accelerated lifetime (as shown in FIG. 3) was 8h (actual lifetime was about 1732 days).
Comparative example 2
Ti/Sb-SnO2/CNT-PbO2The preparation method of the electrode comprises the following steps:
(1) matrix pretreatment: putting a titanium substrate (adopting a TA2 titanium sheet, the size of which is 1cm multiplied by 1cm and the thickness of which is 1mm) into distilled water, ultrasonically cleaning for 30min, soaking the cleaned titanium substrate into a NaOH solution with the mass fraction of 40%, alkaline cleaning for 2h at 80 ℃, then soaking the titanium substrate after alkaline cleaning in the distilled water, ultrasonically cleaning for 30min, then placing the titanium substrate into an oxalic acid solution with the mass fraction of 30%, acid etching for 2h at 98 ℃ to form a uniform pitted surface, enhancing the bonding force between the titanium substrate and a metal oxide film layer, completely washing the etched titanium substrate with distilled water, and then placing the titanium substrate into absolute ethyl alcohol for later use;
(2) preparing an intermediate layer: 5g of SnCl4·5H2O and 0.3g of SbCl3Dissolving in 25mL of isopropanol, and adding 2.5mL of concentrated hydrochloric acid to prevent hydrolysis to obtain an intermediate layer coating solution; soaking the titanium substrate pretreated in the step (1) in the intermediate layer coating solution, drying in a drying oven at 150 ℃ for 10min, then placing in a muffle furnace for firing at 500 ℃ for 10min, repeatedly performing soaking-drying-firing for 10 times, and finally annealing in the muffle furnace at 500 ℃ for 1h to obtain the coating material deposited with Sb-SnO2A titanium substrate of an oxide interlayer;
(3) depositing Sb-SnO obtained in the step (2)2Taking a titanium substrate of the oxide intermediate layer as an anode and graphite with equal area as a cathode, and electrodepositing a surface active layer in 20mL of electroplating solution to obtain Ti/Sb-SnO2/CNT-PbO2An electrode, wherein the plating solution contains 0.5mol/L Pb (NO)3)2，0.01mol/L NaF，1.0mol/L HNO 32g/L carbon nano tube, and the electrodeposition conditions are as follows: current density 20mA/cm2The temperature is 50 ℃, and the electrodeposition time is 1 h.
Tests show that the Ti/Sb-SnO prepared by the method2/CNT-PbO2The oxygen evolution overpotential of the electrode (shown in FIG. 1) was 1.84V and the Tafel slope (shown in FIG. 2) was 0.36.
Comparative example 3
Ti/Sb-SnO2/PVDF-PbO2The preparation method of the electrode comprises the following steps:
(1) matrix pretreatment: putting a titanium substrate (adopting a TA2 titanium sheet, the size of which is 1cm multiplied by 1cm and the thickness of which is 1mm) into distilled water, ultrasonically cleaning for 30min, soaking the cleaned titanium substrate into a NaOH solution with the mass fraction of 40%, alkaline cleaning for 2h at 80 ℃, then soaking the titanium substrate after alkaline cleaning in the distilled water, ultrasonically cleaning for 30min, then placing the titanium substrate into an oxalic acid solution with the mass fraction of 30%, acid etching for 2h at 98 ℃ to form a uniform pitted surface, enhancing the bonding force between the titanium substrate and a metal oxide film layer, completely washing the etched titanium substrate with distilled water, and then placing the titanium substrate into absolute ethyl alcohol for later use;
(2) preparing an intermediate layer: 5g of SnCl4·5H2O and 0.3g of SbCl3Dissolving in 25mL of isopropanol, and adding 2.5mL of concentrated hydrochloric acid to prevent hydrolysis to obtain an intermediate layer coating solution; soaking the titanium substrate pretreated in the step (1) in the intermediate layer coating solution, drying in a drying oven at 150 ℃ for 10min, then placing in a muffle furnace for firing at 500 ℃ for 10min, repeatedly performing soaking-drying-firing for 10 times, and finally annealing in the muffle furnace at 500 ℃ for 1h to obtain the coating material deposited with Sb-SnO2A titanium substrate of an oxide interlayer;
(3) depositing Sb-SnO obtained in the step (2)2Titanium substrate with oxide interlayer as anode, equal-area stoneInk as cathode, and electrodeposition of surface active layer in 20mL of electroplating solution to obtain Ti/Sb-SnO2/PVDF-PbO2An electrode, wherein the plating solution contains 0.5mol/L Pb (NO)3)2，0.01mol/L NaF，1.0mol/L HNO 33g/L polyvinylidene fluoride, and the electrodeposition conditions are as follows: current density 20mA/cm2The temperature is 50 ℃, and the electrodeposition time is 1 h.
Tests show that the Ti/Sb-SnO prepared by the method2/PVDF-PbO2The oxygen evolution overpotential of the electrode (shown in FIG. 1) was 1.86V and the Tafel slope (shown in FIG. 2) was 0.27.
As can be seen from the comparison of example 1 and comparative examples 1 to 3, PVDF and CNT are present in PbO2The co-doping in the active layer improves the oxygen evolution overpotential of the prepared electrode and reduces the tafel slope of the electrode, which shows that the co-doping of PVDF and CNT improves the catalytic activity of the lead dioxide electrode, and the oxygen evolution activity during the co-doping is superior to the situation of the two single doping.
Comparing example 1 with comparative example 1, it can be seen that the lifetime of the electrode made by co-doping PVDF with CNT is about 1.5 times that before doping.
It should be understood that the detailed description of the invention is merely illustrative of the invention and is not intended to limit the invention to the specific embodiments described. It will be appreciated by those skilled in the art that the present invention may be modified or substituted equally as well to achieve the same technical result; as long as the use requirements are met, the method is within the protection scope of the invention.

Claims (9)

1. Ti/Sb-SnO2/PVDF-CNT-PbO2The preparation method of the electrode is characterized by comprising the following steps:
(1) matrix pretreatment: putting a titanium substrate into distilled water, ultrasonically cleaning, soaking the cleaned titanium substrate into a NaOH solution with the mass fraction of 30-50%, carrying out alkali cleaning at 50-80 ℃ for 2h, then soaking the titanium substrate after the alkali cleaning in the distilled water, ultrasonically cleaning, then putting the titanium substrate into an oxalic acid solution with the mass fraction of 10-30%, carrying out acid etching at 80-100 ℃ for 2h to form uniform pitted surface, washing the etched titanium substrate with distilled water, and putting the cleaned titanium substrate into absolute ethyl alcohol for later use;
(2) preparing an intermediate layer: adding 3-10 g SnCl4·5H2O and 0.2 to 0.5g of SbCl3Dissolving in 25mL of isopropanol, and adding 2.5mL of concentrated hydrochloric acid to obtain an intermediate layer coating solution; soaking the titanium substrate pretreated in the step (1) in the intermediate layer coating solution, drying in a drying oven at 150 ℃ for 10min, then placing in a muffle furnace for firing at 500 ℃ for 10min, repeatedly performing soaking-drying-firing operations for several times, and finally annealing in the muffle furnace at 500 ℃ for 1h to obtain the coating material deposited with Sb-SnO2A titanium substrate of an oxide interlayer;
(3) depositing Sb-SnO obtained in the step (2)2Taking a titanium substrate of the oxide intermediate layer as an anode and graphite with equal area as a cathode, and electrodepositing a surface active layer in electroplating solution to obtain Ti/Sb-SnO2/PVDF-CNT-PbO2An electrode, wherein the plating solution contains Pb (NO)3)2，NaF，HNO3Carbon nano tube and polyvinylidene fluoride, and the electrodeposition conditions are as follows: the current density is 10-80 mA/cm2The temperature is 50-80 ℃, and the electrodeposition time is 0.5-1 h.
2. The method for preparing an electrode according to claim 1, wherein Pb (NO) in the step (3)3)2The concentration is 0.5 to 1.0 mol/L.
3. The method of claim 1, wherein the concentration of NaF in step (3) is 0.01 to 0.05 mol/L.
4. The method of claim 1, wherein the HNO in step (3) is selected from the group consisting of3The concentration is 0.5 to 1.0 mol/L.
5. The method of claim 1, wherein the concentration of the carbon nanotubes in the step (3) is 0 to 4 g/L.
6. The method of claim 1, wherein the concentration of the polyvinylidene fluoride in the step (3) is 0 to 4 g/L.
7. The method of claim 1, wherein the titanium substrate of step (1) is TA2 titanium sheet.
8. The method of claim 1, wherein the number of repetitions is 10.
9. An electrode produced by the production method according to any one of claims 1 to 8.
CN202010087985.1A 2020-02-12 2020-02-12 Ti/Sb-SnO2/PVDF-CNT-PbO2Electrode and method for producing same Pending CN111254435A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202010087985.1A CN111254435A (en) 2020-02-12 2020-02-12 Ti/Sb-SnO2/PVDF-CNT-PbO2Electrode and method for producing same

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202010087985.1A CN111254435A (en) 2020-02-12 2020-02-12 Ti/Sb-SnO2/PVDF-CNT-PbO2Electrode and method for producing same

Publications (1)

Publication Number Publication Date
CN111254435A true CN111254435A (en) 2020-06-09

Family

ID=70945560

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202010087985.1A Pending CN111254435A (en) 2020-02-12 2020-02-12 Ti/Sb-SnO2/PVDF-CNT-PbO2Electrode and method for producing same

Country Status (1)

Country Link
CN (1) CN111254435A (en)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111924941A (en) * 2020-08-11 2020-11-13 河北建设集团安装工程有限公司 Modified PbO2Preparation method of electrode and method for removing BPA through electrocatalysis
CN112158920A (en) * 2020-09-15 2021-01-01 中国南方电网有限责任公司超高压输电公司天生桥局 Anode material suitable for external cold water treatment, preparation method and treatment process
CN113061955A (en) * 2021-03-17 2021-07-02 宜兴禹博治环保科技有限公司 Preparation method of conductive polyaniline modified electrode
CN113562815A (en) * 2021-08-13 2021-10-29 安徽康菲尔检测科技有限公司 Preparation method of composite coating DSA electrode for water treatment and prepared composite coating DSA electrode

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104047020A (en) * 2014-07-03 2014-09-17 环境保护部华南环境科学研究所 Titanium-based doped polyvinylidene fluoride lead dioxide anode plate as well as preparation method and application thereof

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104047020A (en) * 2014-07-03 2014-09-17 环境保护部华南环境科学研究所 Titanium-based doped polyvinylidene fluoride lead dioxide anode plate as well as preparation method and application thereof

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
XIAOYUE DUAN 等: "Comparative studies on the electro-catalytic oxidation performance of surfactant-carbon nanotube-modified PbO2 electrodes", 《JOURNAL OF ELECTROANALYTICAL CHEMISTRY》 *

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111924941A (en) * 2020-08-11 2020-11-13 河北建设集团安装工程有限公司 Modified PbO2Preparation method of electrode and method for removing BPA through electrocatalysis
CN112158920A (en) * 2020-09-15 2021-01-01 中国南方电网有限责任公司超高压输电公司天生桥局 Anode material suitable for external cold water treatment, preparation method and treatment process
CN112158920B (en) * 2020-09-15 2022-06-03 中国南方电网有限责任公司超高压输电公司天生桥局 Anode material suitable for external cold water treatment, preparation method and treatment process
CN113061955A (en) * 2021-03-17 2021-07-02 宜兴禹博治环保科技有限公司 Preparation method of conductive polyaniline modified electrode
CN113061955B (en) * 2021-03-17 2023-02-21 宜兴禹博治环保科技有限公司 Preparation method of conductive polyaniline modified electrode
CN113562815A (en) * 2021-08-13 2021-10-29 安徽康菲尔检测科技有限公司 Preparation method of composite coating DSA electrode for water treatment and prepared composite coating DSA electrode

Similar Documents

Publication Publication Date Title
CN111254435A (en) Ti/Sb-SnO2/PVDF-CNT-PbO2Electrode and method for producing same
CN110040820B (en) Titanium-based tin antimony oxide electrode modified by titanium dioxide net structure and preparation method thereof
CN105621541A (en) Transition-metal doped lead dioxide electrode for wastewater treatment as well as preparation method and application thereof
CN104591342B (en) For the Ti/Ebonex/PbO of advanced treatment of wastewater2The preparation method of electrode
CN105110425A (en) Preparation method of carbon-nanotube-modified three-dimensional porous-titanium-base lead dioxide electrode
CN109778100B (en) Long-life energy-saving dimensionally stable PbO2Arc thermal spraying preparation method of anode intermediate layer
CN113690455B (en) Long-life anode electrode material and preparation method thereof
CN111334837A (en) Nickel-doped titanium dioxide nanotube modified tin-antimony electrode and preparation method thereof
CN106395999A (en) Ni-doped tin dioxide microporous anode, preparation method and application
CN113264573B (en) Bipolar electrode, preparation method thereof and wastewater treatment system
CN110980890A (en) Titanium-based lead dioxide electrode for degrading rhodamine B and preparation method and application thereof
CN106835193A (en) A kind of Pb bases/3D PbO2/MeOx composite anodes and preparation method thereof
CN111924941A (en) Modified PbO2Preparation method of electrode and method for removing BPA through electrocatalysis
CN113072137A (en) Interlayer modified titanium-based lead oxide electrode and preparation method and application thereof
CN116282395A (en) Method for preparing carbon nano tube modified tin-antimony electrode through electrodeposition in eutectic solvent
CN111186883B (en) Novel preparation technology of lead dioxide electrode modified by titanium tetroxide nanotube
CN106809918A (en) A kind of carbon nano tube modified lead dioxide electrode and preparation method thereof
CN112429813B (en) Blue-TiO doped with carbon nano tube 2 /CNT-PbO 2 Preparation method of electrode material
CN111926345B (en) IrO2-Ta2O5 anode with TiN nanotube interlayer
CN111943327B (en) Having RuO for acidic wastewater treatment2-IrO2Electrode material of intermediate layer and preparation method
CN108301013A (en) A kind of preparation method for the modified anode of lead dioxide generating ozone
JP2008138282A (en) Anode for alkaline electrolysis
CN113233549A (en) Nano lead dioxide electrode and preparation method and application thereof
CN112250229A (en) Preparation method and application of electrode with high catalytic activity and stability
CN113061955B (en) Preparation method of conductive polyaniline modified electrode

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
RJ01 Rejection of invention patent application after publication

Application publication date: 20200609

RJ01 Rejection of invention patent application after publication