WO2018023912A1 - Électrode au dioxyde de plomb à base de titane dopée à l'indium, et son procédé de fabrication et son application - Google Patents

Électrode au dioxyde de plomb à base de titane dopée à l'indium, et son procédé de fabrication et son application Download PDF

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WO2018023912A1
WO2018023912A1 PCT/CN2016/109462 CN2016109462W WO2018023912A1 WO 2018023912 A1 WO2018023912 A1 WO 2018023912A1 CN 2016109462 W CN2016109462 W CN 2016109462W WO 2018023912 A1 WO2018023912 A1 WO 2018023912A1
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electrode
titanium
pbo
doped
solution
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Chinese (zh)
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陈建孟
戴启洲
夏伊静
王家德
乔志华
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浙江工业大学
宝鸡市昌立特种金属有限公司
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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
    • 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
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D9/00—Electrolytic coating other than with metals
    • C25D9/04—Electrolytic coating other than with metals with inorganic materials
    • 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
    • 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

Definitions

  • the invention relates to a main group metal indium (In) doped titanium-based lead dioxide electrode and a preparation method and application thereof, the electrode has high catalytic performance and can be applied to electrochemical degradation of biodegradable pharmaceutical wastewater, belonging to electrochemical Technical and environmentally friendly wastewater treatment technology.
  • the key and core of electrochemical water treatment technology is the performance of anode materials.
  • the anode material In addition to the low cost of preparation, the anode material must also have the characteristics of good electrical conductivity, high oxygen evolution potential and good catalytic activity for electrochemical oxidation treatment of organic pollutants in wastewater.
  • the lead dioxide electrode has the advantages of good electrical conductivity, low cost, simple preparation method, high oxygen evolution potential and strong oxidizing ability, and is an electrode material which is generally considered to have application prospects.
  • Lead dioxide electrodes are typically produced by electrodeposition on ceramic, titanium metal and other metal material substrates. Because titanium has good corrosion resistance, low price, small thermal conductivity, easy surface physical and chemical processing, it is an ideal base material for the preparation of lead dioxide electrode. At present, titanium-based lead dioxide electrodes have been successfully applied to the production of inorganic and organic compounds, environmental pollution control.
  • the PbO 2 active layer is not tightly bonded to the matrix, the PbO 2 active layer has large stress, and is easily peeled off, which affects the catalytic activity and stability of the electrode.
  • some research work has further improved the titanium-based lead dioxide electrode.
  • One method is to introduce a tin and tantalum intermediate layer as a transition layer between the titanium substrate and the lead dioxide active layer, which can greatly reduce the internal stress between the lead dioxide active layer and the titanium substrate.
  • Another method is to add NaF and polytetrafluoroethylene (PTFE) to the plating solution to prepare a fluorine-containing lead dioxide electrode, and the prepared electrode has the advantages of small internal stress, good bonding force and long electrode life.
  • PTFE polytetrafluoroethylene
  • An In-doped titanium-based lead dioxide electrode wherein the electrode is made of titanium, and the tin-germanium oxide underlayer, the ⁇ -PbO 2 intermediate layer, and the doped indium are sequentially plated from the inside to the outside of the titanium substrate. Fluorine ⁇ -PbO 2 active layer.
  • the preparation method of the In doped titanium-based lead dioxide electrode of the invention comprises: roughening the surface of the titanium substrate, preparing the tin antimony oxide underlayer by thermal decomposition on the surface of the roughened titanium substrate, and then performing alkaline
  • the In-doped titanium-based lead dioxide electrode is prepared by electroplating an ⁇ -PbO 2 intermediate layer and finally doping a fluorine-containing ⁇ -PbO 2 active layer by acid composite plating.
  • the titanium substrate may be a titanium sheet, a titanium mesh or a titanium tube.
  • the method for preparing the In-doped titanium-based lead dioxide electrode is carried out as follows:
  • Titanium matrix pretreatment surface roughening treatment
  • the surface of the titanium substrate is sanded with sandpaper, the lye is degreased, washed with water, placed in a sulfuric acid solution, immersed and etched at 50-70 ° C for 10 to 60 minutes, washed with water, and then placed in an oxalic acid solution at 70-90. Soaking and etching at °C for 2 to 5 hours, and washing with water to obtain a pretreated titanium substrate;
  • the tin antimony oxide sol solution is uniformly coated on the surface of the pretreated titanium substrate obtained in the step (1), placed in a tube muffle furnace, baked at a constant temperature of 130 ° C for 20 min, and then heated to 515 ° C. Thermal decomposition treatment for 15 min, cooling, completing an operation cycle;
  • the tin antimony oxide sol solution is prepared by mixing the following parts by weight: 5 to 10 parts of SbCl 3 , 95 to 110 parts of SnCl 4 ⁇ 5H 2 O, 268 to 290 parts of ethylene glycol, and 180 to 200 parts of citric acid. ;
  • the tin antimony oxide sol solution is prepared by mixing the following parts by weight of materials: 7.53 parts of SbCl 3 , 104.16 parts of SnCl 4 ⁇ 5H 2 O, 280 parts of ethylene glycol, and 192.14 parts of citric acid;
  • the electrode plated with the tin antimony oxide underlayer prepared by the step (2) is an anode, and the titanium piece is a cathode, and is placed in an alkaline plating solution for constant current electrodeposition of the ⁇ -PbO 2 intermediate layer, and the operating condition is: temperature 50 ⁇ 65 ° C (preferably 60 ° C), current density of 3 ⁇ 5 mA / cm 2 (preferably 5 mA / cm 2 ), deposition time of 0.5 ⁇ 2h (preferably 1h); obtained tin-bismuth oxide underlayer and ⁇ -PbO 2 intermediate layer Electrode
  • the alkaline plating solution is prepared according to the following composition: PbO 0.1 mol/L, NaOH 4-5 mol/L, and the solvent is water;
  • the electrode plated with the tin antimony oxide underlayer and the ⁇ -PbO 2 intermediate layer prepared in the step (3) is used as an anode, and the titanium piece is used as a cathode, and is placed in an acidic plating solution to carry out constant current electrodeposition of the doped fluorine-containing ⁇ . -PbO 2 surface active layer, operating conditions: temperature 50 ⁇ 90 ° C (preferably 80 ° C), current density 10 ⁇ 80 mA / cm 2 (preferably 50 mA / cm 2 ), deposition time 1.5 ⁇ 2h (preferably 2h), obtained The In doped titanium-based lead dioxide electrode;
  • the acidic plating solution is prepared as follows:
  • the mixture was first prepared as follows: Pb(NO 3 ) 2 0.3 mol/L, KF ⁇ 2H 2 O 0.01 to 0.02 mol/L, In(NO 3 ) 3 0.0015 to 0.012 mol/L, 60 wt% polytetrafluoroethylene 4 ⁇ 5mL / L of the emulsion, the solvent is water; the prepared mixture is adjusted to a pH of 1.5 to 2.0 with nitric acid to obtain the acidic plating solution;
  • the acidic plating solution is prepared as follows:
  • the mixture was prepared as follows: Pb(NO 3 ) 2 0.3 mol/L, KF ⁇ 2H 2 O 0.01 mol/L, In(NO 3 ) 3 0.003 mol/L, 60 wt% polytetrafluoroethylene emulsion 4 mL/L
  • the solvent is water; the prepared mixture is adjusted to a pH of 1.8 with nitric acid to obtain the acidic plating solution;
  • the 60 wt% polytetrafluoroethylene emulsion is commercially available directly.
  • step (1) is operated as follows:
  • the surface of the titanium substrate is sanded with a sandpaper, and then generally ground with a 120-mesh coarse sandpaper, and then polished with a 600-mesh, 1200-mesh fine sandpaper until the surface of the titanium substrate exhibits a silver-white metallic luster.
  • the tin antimony oxide sol solution is uniformly applied to the surface of the pretreated titanium substrate, and the coating method may be brushing, spraying or immersing and centrifuging, which is a person skilled in the art. A well-known technique.
  • the In-doped titanium-based lead dioxide electrode of the invention has strong catalytic activity, high oxygen evolution potential, good stability and long service life, and can be applied to degradation treatment of high concentration biodegradable pharmaceutical wastewater;
  • the method comprises the following steps: using the In-doped titanium-based lead dioxide electrode as the anode and the titanium plate as the cathode, and using the constant current electrolysis pharmaceutical wastewater.
  • the invention utilizes the main group element In to modify the surface structure of the ⁇ -PbO 2 electroplating layer, and the beneficial effects of the invention are compared with the conventional lead dioxide electrode and the prior art:
  • the present invention modifies a lead dioxide electrode by electrode structure design and surface doping: doping a certain amount of main group metal In in a lead nitrate solution containing a fluororesin polymer, using constant current electrochemical deposition
  • a Ti/Sn-SbO x / ⁇ -PbO 2 /In- ⁇ -PbO 2 electrode was prepared.
  • the PbO 2 particles on the electrode surface are more closely dispersed, which greatly improves the structure and properties of the electrode surface, and reduces the internal stress between the PbO 2 active layer and the titanium matrix. Small, therefore, the resulting electrode has a higher oxygen evolution potential and electrochemical stability, effectively extending the life of the electrode.
  • the doping of the main group metal In by the present invention not only improves the catalytic activity of the electrode, but also prolongs the life of the electrode. Through the improvement of surface structure, the particle size of PbO 2 crystal is reduced, and the specific surface area of the electrode is increased, thereby effectively increasing the active site on the electrode surface. Compared with the undoped lead dioxide electrode, the catalytic activity of the modified electrode is obvious. improve.
  • the lead dioxide electrode prepared by the invention having high oxygen evolution potential, high service life and high catalytic activity has an efficient removal effect on the biodegradable pharmaceutical wastewater.
  • the electrode has good catalytic performance, long service life, strong practicability, easy preparation, and broad market prospect.
  • Example 1a is an SEM image (magnification 100 times) of the In-doped PbO 2 electrode prepared in Example 1;
  • 1b is an SEM image of an In-doped PbO 2 electrode prepared in Example 1 (magnification 500 times);
  • FIG 2 is In Preparation Example 1 doped undoped In the XRD pattern of PbO 2 electrode of PbO 2 electrode prepared in Comparative Example 1, wherein, (A) an undoped In the graph of PbO 2 electrode, (B The figure is an In doped PbO 2 electrode;
  • FIG. 3 is a polarization diagram of an In-doped PbO 2 electrode prepared in Example 1 and an undoped In-PbO 2 electrode prepared in Comparative Example 1;
  • Figure 4a is described in Example 2 of PbO 2 electrode In-doped and undoped In the degradation effect of PbO 2 electrode of 500mg / L aspirin (aspirin removal) comparison chart;
  • Example 2 Figure 4b the degradation of PbO 2 In-doped and undoped In the electrode of PbO 2 electrode 500mg / L aspirin (COD removal efficiency and current efficiency) comparison chart;
  • Example 5 is different from the In-doped PbO 2 electrode 3 and undoped In the PbO 2 electrode degradation effect of 500mg / L aspirin comparison chart.
  • the 60 wt% polytetrafluoroethylene emulsion used below was purchased from Hangzhou Wannengda Technology Co., Ltd.
  • Titanium substrate pretreatment a pure titanium sheet having a thickness of 0.1 mm and a size of 14 cm 2 (7 cm ⁇ 2 cm) is sequentially ground with 120 mesh, 600 mesh and 1200 mesh sandpaper until the titanium matrix exhibits a silvery white metallic luster.
  • Ion water rinse soak the cleaned titanium sheet in a 40% NaOH solution for 30 min, rinse with deionized water; then at 60 ° C in H 2 SO 4 solution (mass score 20 Soak for 20min in %), take it out and wash it with deionized water; finally, soak it in oxalic acid solution (mass fraction 15%) at 80 °C for 3h, rinse with plenty of distilled water to remove oxalic acid and oxalic acid remaining on the surface of titanium substrate.
  • oxalic acid solution mass fraction 15%
  • the tin antimony oxide sol solution was prepared as follows: 7.53 g SbCl 3 , 104.16 g SnCl 4 ⁇ 5H 2 O, 251 mL ethylene glycol, and 192.14 g citric acid.
  • Alkaline electroplating ⁇ -PbO 2 layer the electrode plated with the tin antimony oxide underlayer prepared by the step (2) is an anode, the titanium plate of the same area is a cathode, and is placed in an alkaline electroplating solution
  • the ⁇ -PbO 2 intermediate layer was deposited.
  • the electrode spacing was 6 cm during electrodeposition, the temperature was 60 ° C, the current density was 5 mA cm -2 , and the deposition time was 1 hour.
  • the intermediate layer of tin-bismuth oxide and ⁇ -PbO 2 were prepared. The electrode of the layer.
  • alkaline plating baths prepared according to the following composition: PbO is 0.1mol L -1, NaOH is 4.5mol L -1, the solvent is water.
  • Acid composite plating doped fluorine-containing ⁇ -PbO 2 active layer the electrode plated with the tin antimony oxide underlayer and the ⁇ -PbO 2 intermediate layer prepared in the step (3) is used as an anode, and the same area
  • the titanium sheet is a cathode, and a fluorine-doped ⁇ -PbO 2 surface active layer doped with In is electrolessly deposited in an acidic plating solution.
  • the electrode spacing is 6 cm at the time of electrodeposition, the temperature is 80 ° C, and the current density is 50 mA cm -2 .
  • a product In doped titanium-based lead dioxide electrode was prepared.
  • the acidic plating solution is prepared as follows: firstly, the mixed liquid is prepared as follows: Pb(NO 3 ) 2 is 0.3 mol L -1 , KF ⁇ 2H 2 O is 0.01 mol L -1 , In(NO 3 ) 3 is 0.003 mol L -1 , 60% polytetrafluoroethylene emulsion (PTFE) 4 mL L -1 , the solvent is water, to obtain a mixed solution; the prepared mixture is adjusted to pH 1.8 with HNO 3 . That is, an acidic plating solution is obtained.
  • the In (NO 3 ) 3 is not added to the acidic plating solution, and the acidic plating solution is prepared as follows:
  • the mixed solution is prepared as follows: Pb(NO 3 ) 2 is 0.3 mol L -1 , KF ⁇ 2H 2 O is 0.01 mol L -1 , and the mass fraction is 60% polytetrafluoroethylene emulsion (PTFE) 4 mL L -1 , the solvent is water, and the mixture is obtained.
  • the prepared mixture was adjusted to pH 1.8 with HNO 3 to obtain an acidic plating solution.
  • the other steps and operations were the same, and a titanium-based lead dioxide electrode not doped with In was obtained.
  • the In-doped PbO 2 electrode prepared in Example 1 was characterized by field emission scanning electron microscopy (SEM), see Figures 1a, 1b. It can be seen from Fig. 1a, 1b that the surface of the prepared electrode exhibits a distinct tetrahedral three-dimensional crystal structure, the grain distribution is dense and uniform, and the particle size is about 35 ⁇ m. 2 is an XRD pattern of an In-doped PbO 2 electrode and an undoped PbO 2 electrode. Comparing the ⁇ -PbO 2 standard card, the surface active layer of the prepared In-doped lead dioxide electrode is ⁇ -PbO 2 .
  • the crystal structure of the tetragonal body, and the crystallinity and crystallization orientation after doping with In is slightly different. It is known that the half-peak of the main crystal plane ⁇ (200) of the doped electrode and the undoped electrode is calculated by the Xie Le formula. After doping with In, the particle size of the PbO 2 crystal is reduced, which helps to increase the activity of the electrode surface. Site, thereby increasing the catalytic activity of the electrode. In addition, the incorporation of In does not introduce a new phase, indicating that In may enter the ⁇ -PbO 2 lattice in a replacement or interstitial manner to form a solid solution, which causes the diffraction peak to change.
  • a three-electrode electrochemical measurement system was used.
  • the prepared In-doped lead dioxide electrode and the undoped lead dioxide electrode were used as the working electrode (10 mm ⁇ 10 mm), and the platinum electrode was used as the auxiliary electrode. (10 mm ⁇ 15 mm), a saturated calomel electrode (SCE) was used as a reference electrode, and the polarization curve of the electrode was measured in a 0.5 mol L -1 H 2 SO 4 solution, as shown in Fig. 3.
  • the oxygen evolution potential of the In-doped lead dioxide electrode was measured to be about 2.08 V, which was higher than that of the undoped Indium dioxide electrode (1.99 V).
  • the oxygen evolution reaction is a major competitive side reaction, which leads to waste of electrical energy and reduces the effective utilization of current.
  • the higher oxygen evolution potential can effectively inhibit the occurrence probability of oxygen evolution side reactions.
  • the oxygen evolution potential is beneficial to improve current efficiency.
  • the as-doped lead dioxide electrode prepared in Example 1 and the undoped Indium dioxide electrode prepared in Comparative Example 1 were subjected to electrocatalytic oxidation degradation of aspirin.
  • the In-doped lead dioxide electrode prepared in Example 1 or the undoped Indium dioxide electrode prepared in Comparative Example 1 was used as the anode, the titanium sheet was the cathode, the electrode area was 14 cm 2 , and the electrochemical degradation was performed by constant current electrolysis. .
  • the constant current density is 50 mA cm -2 and the electrode spacing is 4 cm.
  • 500 mg L -1 aspirin containing 0.1 mol L -1 electrolyte Na 2 SO 4 was used as the simulated wastewater, the reaction volume was 250 mL, and the wastewater treatment was carried out under the action of magnetic stirring, and the degradation reaction was carried out at different times for sampling analysis.
  • the changes in the concentration of aspirin at different times were determined by high performance liquid chromatography (HPLC).
  • FIG. 4a The change of total organic carbon content (TOC) was measured by TOC meter.
  • the experimental results are shown in Figures 4a and 4b.
  • Figures 4a and 4b show a comparison of the degradation effects of In-doped PbO 2 electrode and undoped PbO 2 electrode on 500 mg L -1 aspirin.
  • Figure 4a shows the removal rate of aspirin and
  • Figure 4b shows the removal rate of TOC.
  • As-doped electrode degradation of aspirin The toxic metal ions that may be generated in electrolysis are detected by plasma gas chromatography (ICP-MS), such as Pb, Ti, Sn, Sb, and In. From the experimental results, it is known that Ti is not detected in the treated wastewater solution. The presence of Sn, Sb and In ions, the concentration of Pb ions is 0.005 mg L -1 , which is much lower than the emission standard of lead ions ( ⁇ 0.1 mg L -1 ). Therefore, the use of In-doped lead dioxide electrode to degrade aspirin is highly safe.
  • ICP-MS plasma gas chromatography
  • Titanium substrate pretreatment a pure titanium sheet having a thickness of 0.1 mm and a size of 14 cm 2 (7 cm ⁇ 2 cm) is sequentially ground with 120 mesh, 600 mesh and 1200 mesh sandpaper until the titanium matrix exhibits a silvery white metallic luster.
  • Ion water rinse soak the cleaned titanium sheet in a 40% NaOH solution for 30 min, rinse with deionized water; then at 60 ° C in H 2 SO 4 solution (mass score 20 Soak for 20min in %), take it out and wash it with deionized water; finally, soak it in oxalic acid solution (mass fraction 15%) at 80 °C for 3h, rinse with plenty of distilled water to remove oxalic acid and oxalic acid remaining on the surface of titanium substrate.
  • oxalic acid solution mass fraction 15%
  • the tin antimony oxide sol solution was prepared as follows: 7.53 g SbCl 3 , 104.16 g SnCl 4 ⁇ 5H 2 O, 251 mL ethylene glycol, and 192.14 g citric acid.
  • step (2) antimony tin oxide electrode prepared by the underlying plating anode, the area of the titanium sheet, etc. as a cathode in an alkaline electroplating bath constant current level
  • the ⁇ -PbO 2 intermediate layer was deposited.
  • the electrode spacing was 6 cm during electrodeposition, the temperature was 60 ° C, the current density was 5 mA cm -2 , and the deposition time was 1 hour.
  • the intermediate layer of tin-bismuth oxide and ⁇ -PbO 2 were prepared. The electrode of the layer.
  • alkaline plating baths prepared according to the following composition: PbO is 0.1mol L -1, NaOH is 4.5mol L -1, the solvent is water.
  • Acid composite plating doped fluorine-containing ⁇ -PbO 2 active layer the electrode plated with the tin antimony oxide underlayer and the ⁇ -PbO 2 intermediate layer prepared in the step (3) is used as an anode, and the same area
  • the titanium sheet is used as a cathode, and the fluorine-containing ⁇ -PbO 2 surface active layer doped with In is subjected to constant current electrodeposition in an acidic plating solution having different In contents.
  • the electrode spacing is 6 cm at the time of electrodeposition, the temperature is 80 ° C, and the current density is 50 mA cm -2 , deposition time is 2 hours, and the product is prepared with different In-doped titanium-based lead dioxide electrodes.
  • the acidic plating solution with different In contents is prepared as follows: firstly, the mixed liquid is prepared as follows: Pb(NO 3 ) 2 is 0.3 mol L -1 , KF ⁇ 2H 2 O is 0.01 mol L -1 , In (NO 3 ) 3 each of 0.0015 mol L -1 , 0.003 mol L -1 , 0.006 mol L -1 and 0.012 mol L -1 , 60% by mass of polytetrafluoroethylene emulsion (PTFE) 4 mL L -1 , The solvent was water to obtain a mixed solution; the prepared mixture was adjusted to pH 1.8 with HNO 3 to obtain an acidic plating solution having different In contents.
  • PTFE polytetrafluoroethylene emulsion
  • the removal rate of aspirin by In-PbO 2 electrode prepared by the concentration of In(NO 3 ) 3 in the electrodeposition solution was 0.003 mol L -1 , which was 76.45% in the electrodeposition solution.
  • the In-PbO 2 electrode prepared at a concentration of In(NO 3 ) 3 of 0 mol L -1 , 0.0015 mol L -1 , 0.006 mol L -1 and 0.012 mol L -1 was 1.19, 1.06, 1.12 and 1.26 times.
  • a first-order reaction kinetics fit was performed on the degradation process of aspirin to obtain an ln(C/C0) ⁇ t curve, as shown in the inset of FIG.
  • the concentration of In(NO 3 ) 3 in the electrodeposition solution is 0 mol L -1 , 0.0015 mol L -1 , 0.003 mol L -1 , 0.006 mol L -
  • the degradation rate constants of aspirin on the In-PbO 2 electrode prepared at 1 and 0.012 mol L -1 were 1.2 ⁇ 10 -4 s -1 , 1.5 ⁇ 10 -4 s -1 , and 1.7 ⁇ 10 -4 s -1 , respectively.

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Abstract

La présente invention décrit une électrode au dioxyde de plomb à base de titane dopée à l'indium (In), et son procédé de fabrication, et son application dans le traitement de dégradation des eaux usées pharmaceutiques fortement concentrées avec une faible biodégradabilité. L'électrode utilise du titane comme matrice, et comprend une couche de base d'oxyde d'antimoine-étain, une couche médiane d'α-PbO2, et dopée à l'In, une couche active de β-PbO2 contenant du fluorure, les couches étant revêtues sur une matrice de titane dans cet ordre. Une conception structurale et un dopage de surface de l'électrode sont utilisés pour modifier l'électrode au dioxyde de plomb. En ajoutant le métal post-transition (In) et une résine polymère fluorure, la dispersion de micro-particules de PbO2 sur la surface de l'électrode devient plus compacte et uniforme, améliorant grandement une structure de surface et la propriété de l'électrode et réduisant une contrainte interne entre la couche active de PbO2 et la matrice de titane. L'électrode finale par conséquent présente un potentiel de dégagement d'oxygène et une stabilité électrochimique supérieurs, prolongeant efficacement la durée de vie utile de l'électrode. L'électrode présente une excellente performance catalytique, une longue durée de vie utile, et une forte applicabilité potentielle, et est facile à fabriquer. L'invention présente de grandes perspectives commerciales.
PCT/CN2016/109462 2016-08-05 2016-12-12 Électrode au dioxyde de plomb à base de titane dopée à l'indium, et son procédé de fabrication et son application WO2018023912A1 (fr)

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