CN110980890A - Titanium-based lead dioxide electrode for degrading rhodamine B and preparation method and application thereof - Google Patents
Titanium-based lead dioxide electrode for degrading rhodamine B and preparation method and application thereof Download PDFInfo
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Abstract
The invention belongs to the field of electrochemical catalytic oxidation water treatment, and relates to a titanium-based lead dioxide electrode for degrading rhodamine B, and a preparation method and application thereof. The titanium-based lead dioxide electrode comprises a titanium substrate, a tin-antimony oxide layer and an active layer (Ce and SDBS are co-doped); the preparation method of the electrode comprises the step of directly carrying out PbO on a titanium substrate on which a tin-antimony oxide bottom layer is thermally deposited2The deposition of the active layer eliminates α -PbO2The preparation process of the layer simplifies the preparation process of the titanium-based lead dioxide electrode, thereby improving the preparation efficiency of the titanium-based lead dioxide electrode, and because α -PbO is cancelled2The layer preparation process, the need for adjustment in this process and the corresponding elimination ofThe controlled technological parameters are beneficial to the improvement of the qualification rate of finished products, the production cost is reduced, and simultaneously, the high oxygen evolution potential, the catalytic activity and the strengthened service life of the titanium-based lead dioxide electrode are greatly improved.
Description
Technical Field
The invention belongs to the field of electrochemical catalytic oxidation water treatment, and relates to a titanium-based lead dioxide electrode for degrading rhodamine B, and a preparation method and application thereof.
Background
Dyes are indispensable industrial products, widely used in many fields, but have toxicity, mutagenicity and carcinogenicity. A large amount of dye-containing wastewater generated in the industrial process is discharged into the natural environment, causing serious environmental pollution and adverse health effects. Many dyes have complex chemical compositions and toxicity and are very stable and therefore difficult to chemically or biologically degrade. More than 60% of dyes are predicted to be produced globally in china. With the rapid development of the dye industry in China, the control of the discharge of high-concentration dye wastewater to a water body becomes a challenge. Thus, there is a pressing need for efficient, low cost techniques for removing these contaminants from wastewater.
At present, methods for removing dye pollutants mainly comprise physical and chemical degradation, Fenton oxidation, adsorption, electrochemical degradation and the like. Among them, electrochemical degradation has attracted people's attention as a feasible, effective, economical, simple and convenient operation method. The emerging electrolysis method has the advantages of no need of adding chemical agents, small equipment volume, small occupied area, no secondary pollution and the like, is concerned, and is used for treating wastewater containing organic pollutants such as alcohol, aldehyde, phenol, dye and the like. According to the requirements of the electrochemical oxidation method water treatment electrode, a novel electrode material with high efficiency, long service life and low energy consumption is needed. And the occurrence of oxygen evolution side reaction needs to be avoided in the electrocatalytic oxidation process, which requires that the anode has higher oxygen evolution potential. Therefore, an electrochemical technology taking a Dimensionally Stable Anode (DSA) as an electrode material is attracting attention, the electrode material overcomes some defects of a traditional graphite electrode, a platinum electrode, a lead-based alloy electrode and the like, as a typical representative of an insoluble anode, a titanium-based lead dioxide electrode is an electrocatalytic electrode which is generally recognized to have great advantages at present, and the titanium-based lead dioxide electrode has the characteristics of high oxygen evolution potential, strong oxidation capacity, good corrosion resistance, good electrical conductivity, capability of passing large current and the like when being electrolyzed in an aqueous solution, so that the titanium-based lead dioxide electrode is widely applied to the fields of water treatment and hydrometallurgy. Although the titanium-based lead dioxide electrode has the advantages, the titanium-based lead dioxide electrode still has a larger space for improvement, and the oxygen evolution potential and the service life of the electrode can be easily improved through modification (coating structure, doping condition and the like).
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a titanium-based lead dioxide electrode for degrading rhodamine B, a preparation method and application thereof, wherein the electrode has a more compact and uniform appearance, a higher oxygen evolution potential, stronger electrocatalytic activity and a longer reinforced service life; the preparation method simplifies the production process and improves the dye sewage treatment effect.
In order to achieve the purpose, the invention provides the following technical scheme:
in a first aspect, the invention provides a titanium-based lead dioxide electrode for degrading rhodamine B, which comprises a titanium-based body layer, a tin-antimony oxide bottom layer and Ce and SDBS co-doped modified PbO sequentially plated from the inside to the outside of the titanium-based body layer2And an active layer.
The titanium substrate can be a titanium wire, a titanium tube, a titanium net, a titanium plate and the like.
In a second aspect, the invention provides a preparation method of a titanium-based lead dioxide electrode for degrading rhodamine B, which specifically comprises the following steps:
1) pretreating a titanium substrate;
2) thermally depositing a tin-antimony oxide bottom layer;
3) electrodeposition of Ce, SDBS codoped modified PbO2Activity ofLayer (b): electrodepositing an active layer in a nitric acid system by taking a titanium substrate with a tin-antimony oxide coating subjected to thermal deposition as an anode and a titanium substrate as a cathode, wherein the nitric acid system contains Ce, SDBS, lead nitrate and copper nitrate; the current density of the electrodeposition is 100 to 300A/m2The electrodeposition temperature is 30-70 ℃, and the electrodeposition time is 1-4 h.
Further, the step 1) of titanium substrate pretreatment specifically comprises the following steps:
firstly, cutting and sand blasting a titanium substrate, and removing surface oxide skin; and then ultrasonically removing oil in an ethanol solution for 10-20 min, etching the solution in a slightly boiling oxalic acid solution for 1-3 h, and washing the etched solution with deionized water for later use.
Further, the concentration of the oxalic acid solution is 3% -10%.
Further, the step 2) of thermally depositing the tin antimony oxide bottom layer specifically comprises the following steps:
2.1) dissolving tin tetrachloride and antimony trichloride in a mixed solution of concentrated hydrochloric acid and ethanol to prepare a coating solution, and coating the coating solution on the surface of the titanium substrate prepared in the step 1);
2.2) drying in a forced air drying oven at the temperature of 100-130 ℃ for 5-10 min;
2.3) repeating the steps 2.1) to 2.2) for 5-9 times, then placing the dried titanium matrix in a muffle furnace, sintering at the temperature of 400-550 ℃ for 50-70 min, taking out and naturally cooling to room temperature.
Further, the content of each component of the coating liquid in the step 2.1) is 40-60 g/L concentrated hydrochloric acid, 450-600 g/L ethanol, 60-100 g/L stannic chloride and 20-40 g/L antimony trichloride.
Further, the step 3) comprises:
preparing a mixed solution of lead nitrate and copper nitrate in an electrolytic bath, heating to 30-70 ℃, adding two doping agents Ce and SDBS, and uniformly stirring to form an acidic deposition solution; and then respectively fixing the titanium substrate anode and the titanium plate cathode of the hot-deposited tin-antimony oxide coating in an electrolytic bath, and electrifying and depositing for 1-4 h.
Further, the acidic deposition solution is prepared by deionized water, wherein the acidic deposition solution contains 100-150 g/mlLPb2+，60～100g/L Cu2+，1～8mmol/L Ce3+And 1-40 mg/L SDBS.
In a third aspect, the invention also provides application of the titanium-based lead dioxide electrode for degrading rhodamine B in dye wastewater.
Further, the dye wastewater contains neutral red or methyl orange or rhodamine B.
Compared with the prior art, the technical scheme provided by the invention has the following beneficial effects: the preparation method of the titanium-based lead dioxide electrode provided by the invention directly carries out PbO on a titanium substrate on which a tin-antimony oxide bottom layer is thermally deposited2The deposition of the active layer eliminates α -PbO2The preparation process of the layer simplifies the preparation process of the titanium-based lead dioxide electrode, thereby improving the preparation efficiency of the titanium-based lead dioxide electrode, and because α -PbO is cancelled2The preparation process of the layer correspondingly cancels the technological parameters which need to be adjusted and controlled in the process, is beneficial to improving the finished product qualification rate of the product, thereby reducing the production cost, and simultaneously greatly improving the high oxygen evolution potential, the catalytic activity and the strengthened service life of the electrode.
In addition, due to the conventional anode PbO2The active layer has low adhesive force on the titanium matrix, is easy to peel off, and has short service life in the electrolytic process2An intermediate layer is introduced between the two layers, and the intermediate layer plays a role in adding PbO on one hand2The layer is well bonded on the substrate, on the other hand, the corrosion of the titanium substrate can be effectively slowed down, and meanwhile, the surface appearance of the anode can be effectively improved and the catalytic activity of the anode is improved by co-doping Ce and SDBS with the modified lead dioxide anode.
Drawings
FIG. 1 is a schematic diagram of the preparation process and application of a titanium-based lead dioxide electrode for degrading rhodamine B provided by the invention;
FIGS. 2(a) and 2(b) are comparative scanning electron microscope images of undoped and co-doped modified electrodes provided in example 1 of the present invention;
FIG. 3 is a comparison graph of linear sweep voltammograms of undoped and co-doped modified electrodes provided in example 1 of the present invention;
FIG. 4 is a plot of cyclic voltammetry for undoped and co-doped modified electrodes provided in example 1 of the present invention;
FIGS. 5(a) and 5(B) are graphs comparing the removal rates of rhodamine B and COD, respectively, for undoped and co-doped modified electrodes provided in example 1 of the present invention;
fig. 6 is a graph comparing the enhanced lifetimes of undoped and codoped modified electrodes provided in example 1 of the present invention.
Detailed Description
Reference will now be made in detail to the exemplary embodiments, examples of which are illustrated in the accompanying drawings. When the following description refers to the accompanying drawings, like numbers in different drawings represent the same or similar elements unless otherwise indicated. The embodiments described in the following exemplary embodiments do not represent all embodiments consistent with the present invention. Rather, they are merely examples of methods consistent with certain aspects of the invention, as detailed in the appended claims.
In order to make those skilled in the art better understand the technical solution of the present invention, the following detailed description of the present invention is provided with reference to the accompanying drawings and examples.
Example 1:
referring to fig. 1, the invention provides a titanium-based lead dioxide electrode for degrading rhodamine B, which comprises a titanium-based body layer, a tin-antimony oxide bottom layer and Ce and SDBS codoped modified PbO sequentially plated from the inside to the outside of the titanium-based body layer2The active layer is prepared by the following specific steps:
1) pretreating a titanium substrate;
2) thermally depositing a tin-antimony oxide bottom layer;
3) electrodeposition of Ce, SDBS codoped modified PbO2Active layer: electrodepositing an active layer in a nitric acid system by taking a titanium substrate with a tin-antimony oxide coating subjected to thermal deposition as an anode and a titanium substrate as a cathode, wherein the nitric acid system contains Ce, SDBS, lead nitrate and copper nitrate; the current density of the electrodeposition is 100 to 300A/m2The electrodeposition temperature is 30-70 ℃, and the electrodeposition time is 1-4 h.
Further, the step 1) of pretreatment of the titanium substrate comprises: firstly, cutting and sand blasting a titanium substrate, and removing surface oxide skin; and then ultrasonically removing oil in an ethanol solution for 10-20 min, etching the solution in a slightly boiling oxalic acid solution for 1-3 h, and washing the etched solution with deionized water for later use.
Wherein, the titanium matrix adopts a titanium net; the concentration of the oxalic acid solution is 3-10%.
Further, step 2) thermal deposition of a tin antimony oxide bottom layer specifically comprises:
2.1) dissolving tin tetrachloride and antimony trichloride in a mixed solution of concentrated hydrochloric acid and ethanol to prepare a coating solution, and coating the coating solution on the surface of the titanium substrate prepared in the step 1);
2.2) drying for 5min in an air-blast drying oven at the temperature of 100 ℃;
2.3) repeating the steps 2.1) to 2.2) for 7 times, then placing the dried titanium matrix in a muffle furnace for sintering at 450 ℃ for 60min, taking out and naturally cooling to room temperature.
Wherein the content of each component of the coating liquid in the step 2.1) is 40-60 g/L concentrated hydrochloric acid, 450-600 g/L ethanol, 60-100 g/L stannic chloride and 20-40 g/L antimony trichloride.
Preferably, step 3) electrodepositing Ce, SDBS co-doped modified PbO2The active layer specifically includes: taking a titanium substrate with a tin-antimony oxide coating subjected to thermal deposition as an anode and a titanium substrate as a cathode, and electrodepositing an active layer in a nitric acid system, wherein the electrodeposition current density is 150A/m2The electrodeposition temperature is 60 ℃, and the electrodeposition time is 1 h.
Wherein the nitric acid system contains 150g/L Pb2+，80g/L Cu2+，4mmol/L Ce3+And 40 mg/LSDBS.
In addition, the invention also provides application of the titanium-based lead dioxide electrode for degrading rhodamine B in dye wastewater, wherein the dye wastewater contains the rhodamine B.
In conclusion, the detection of the undoped titanium-based lead dioxide electrode and the Ce and SDBS co-doped modified titanium-based lead dioxide electrode is as follows:
① referring to FIG. 2, it is an undoped titanium-based lead dioxide electrodeCe. Microscopy (SEM) comparison of SDBS modified titanium-based lead dioxide electrodes. As can be seen from FIG. 2, PbO is coupled via Ce and SDBS2The doping modification of the active layer reduces the particles on the surface of the electrode, the structure becomes more fine and uniform, the compactness of the microstructure is increased, and PbO is reduced2Internal stress of the active layer improves PbO2Stability of the active layer, PbO2The active layer and the tin-antimony oxide bottom layer have better binding capacity, so that the service life of the modified electrode is greatly prolonged.
② referring to FIG. 3, which is a comparison of linear sweep voltammetry curves of undoped titanium-based lead dioxide electrode and Ce, SDBS modified titanium-based lead dioxide electrode, it can be seen from FIG. 3 that PbO is subjected to Ce, SDBS2The electrode with the doped and modified active layer has higher oxygen evolution potential.
③ referring to FIG. 4, which shows a comparison of cyclic sweep voltammetry curves of undoped titanium-based lead dioxide electrode and Ce, SDBS modified titanium-based lead dioxide electrode, it can be seen from FIG. 4 that PbO is subjected to Ce, SDBS2The electrode with the doped and modified active layer has stronger catalytic activity.
④ referring to FIG. 5, it is a comparison graph of rhodamine B removal rate and COD removal rate of undoped titanium-based lead dioxide electrode and Ce, SDBS modified titanium-based lead dioxide electrode, and it can be seen from FIG. 5 that PbO is treated by Ce, SDBS2The electrode with the modified doped active layer has higher rhodamine B removal rate and COD removal rate, the removal rate of the electro-catalytic degradation of rhodamine B can reach 88.0%, and the COD degradation removal rate is 69.4%.
⑤ enhanced life test, tap water is prepared with 1M sulfuric acid, 40 deg.C, and current density of 10000A/M2The strengthening life of the undoped titanium-based lead dioxide electrode is 25min, the strengthening life of the co-doped modified titanium-based lead dioxide electrode is 155min, and the strengthening life of the electrode is improved by 6.2 times, as shown in figure 6.
Example 2:
referring to the figure 1, the invention provides a titanium-based lead dioxide electrode for degrading rhodamine B, which comprises a titanium-based body layer, wherein a tin-antimony oxide bottom layer and Ce,SDBS co-doped modified PbO2The active layer is prepared by the following specific steps:
1) pretreating a titanium substrate;
2) thermally depositing a tin-antimony oxide bottom layer;
3) electrodeposition of Ce, SDBS codoped modified PbO2Active layer: electrodepositing an active layer in a nitric acid system by taking a titanium substrate with a tin-antimony oxide coating subjected to thermal deposition as an anode and a titanium substrate as a cathode, wherein the nitric acid system contains Ce, SDBS, lead nitrate and copper nitrate; the current density of the electrodeposition is 100 to 300A/m2The electrodeposition temperature is 30-70 ℃, and the electrodeposition time is 1-4 h.
Further, the step 1) of pretreatment of the titanium substrate comprises: firstly, cutting and sand blasting a titanium substrate, and removing surface oxide skin; then, ultrasonically removing oil in an ethanol solution for 15min, etching the solution in a slightly boiling oxalic acid solution for 2h, and washing the etched solution with deionized water for later use.
Wherein, the titanium substrate adopts a titanium plate; the concentration of the oxalic acid solution was 5%.
Further, step 2) thermal deposition of a tin antimony oxide bottom layer specifically comprises:
2.1) dissolving tin tetrachloride and antimony trichloride in a mixed solution of concentrated hydrochloric acid and ethanol to prepare a coating solution, and coating the coating solution on the surface of the titanium substrate prepared in the step 1);
2.2) drying in a forced air drying oven at 100 ℃ for 10 min;
2.3) repeating the steps 2.1) to 2.2) for 5 times, then placing the dried titanium matrix in a muffle furnace for sintering at 550 ℃ for 50min, taking out and naturally cooling to room temperature.
Wherein the content of each component of the coating liquid in the step 2.1) is 40-60 g/L concentrated hydrochloric acid, 450-600 g/L ethanol, 60-100 g/L stannic chloride and 20-40 g/L antimony trichloride.
Preferably, step 3) electrodepositing Ce, SDBS co-doped modified PbO2The active layer specifically includes: taking a titanium substrate with a tin-antimony oxide coating subjected to thermal deposition as an anode and a titanium substrate as a cathode, and electrodepositing an active layer in a nitric acid system, wherein the electrodeposition current density is 100A/m2Electric precipitationThe deposition temperature is 70 ℃, and the electrodeposition time is 4 h.
Wherein the nitric acid system contains 100g/L Pb2+，100g/L Cu2+，8mmol/L Ce3+And 20 mg/LSDBS.
In addition, the invention also provides application of the titanium-based lead dioxide electrode for degrading rhodamine B in dye wastewater, wherein the dye wastewater contains neutral red or methyl orange.
Example 3:
referring to fig. 1, the invention provides a titanium-based lead dioxide electrode for degrading rhodamine B, which comprises a titanium-based body layer, a tin-antimony oxide bottom layer and Ce and SDBS codoped modified PbO sequentially plated from the inside to the outside of the titanium-based body layer2The active layer is prepared by the following specific steps:
1) pretreating a titanium substrate;
2) thermally depositing a tin-antimony oxide bottom layer;
3) electrodeposition of Ce, SDBS codoped modified PbO2Active layer: electrodepositing an active layer in a nitric acid system by taking a titanium substrate with a tin-antimony oxide coating subjected to thermal deposition as an anode and a titanium substrate as a cathode, wherein the nitric acid system contains Ce, SDBS, lead nitrate and copper nitrate; the current density of the electrodeposition is 100 to 300A/m2The electrodeposition temperature is 30-70 ℃, and the electrodeposition time is 1-4 h.
Further, the step 1) of pretreatment of the titanium substrate comprises: firstly, cutting and sand blasting a titanium substrate, and removing surface oxide skin; then, ultrasonically removing oil in an ethanol solution for 20min, etching the solution in a slightly boiling oxalic acid solution for 1h, and washing the etched solution with deionized water for later use.
Wherein, the titanium substrate adopts a titanium pipe; the concentration of the oxalic acid solution was 10%.
Further, step 2) thermal deposition of a tin antimony oxide bottom layer specifically comprises:
2.1) dissolving tin tetrachloride and antimony trichloride in a mixed solution of concentrated hydrochloric acid and ethanol to prepare a coating solution, and coating the coating solution on the surface of the titanium substrate prepared in the step 1);
2.2) drying for 5min in a forced air drying oven at the temperature of 130 ℃;
2.3) repeating the steps 2.1) to 2.2) for 9 times, then placing the dried titanium matrix in a muffle furnace to sinter at 400 ℃ for 70min, taking out and naturally cooling to room temperature.
Wherein the content of each component of the coating liquid in the step 2.1) is 40-60 g/L concentrated hydrochloric acid, 450-600 g/L ethanol, 60-100 g/L stannic chloride and 20-40 g/L antimony trichloride.
Preferably, step 3) electrodepositing Ce, SDBS co-doped modified PbO2The active layer specifically includes: taking a titanium substrate with a tin-antimony oxide coating subjected to thermal deposition as an anode and a titanium substrate as a cathode, and electrodepositing an active layer in a nitric acid system, wherein the electrodeposition current density is 300A/m2The electrodeposition temperature is 30 ℃, and the electrodeposition time is 2 h.
Wherein the nitric acid system contains 120g/L Pb2+，80g/L Cu2+，2mmol/L Ce3+And 30 mg/LSDBS.
In addition, the invention also provides application of the titanium-based lead dioxide electrode for degrading rhodamine B in dye wastewater, wherein the dye wastewater contains neutral red or methyl orange.
Therefore, the invention provides the titanium-based lead dioxide electrode (Ti/PbO) for degrading rhodamine B2-Ce-SDBS) which takes titanium wire or titanium tube or titanium net or titanium plate as substrate and takes tin-antimony oxide layer as bottom layer and does not contain α -PbO2An intermediate layer, directly depositing Ce and SDBS doped PbO outside the tin-antimony oxide layer2An active layer; by doping Ce and SDBS, the oxygen evolution potential is improved, and the titanium-based lead dioxide electrode modified by Ce and SDBS improves the electrocatalytic activity, so that the removal rate of degrading rhodamine B is improved; compared with the common titanium-based lead dioxide in the prior art, the Ce and SDBS modified titanium-based lead dioxide electrode provided by the invention has the advantages of more compact and uniform appearance, higher electrocatalysis performance and longer strengthening service life, the strengthening service life is prolonged by 6.3 times, the removal rate of electrocatalysis degradation rhodamine B can reach 88.0%, and the removal rate of COD degradation is 69.4%.
The foregoing are merely exemplary embodiments of the present invention, which enable those skilled in the art to understand or practice the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention.
It is to be understood that the present invention is not limited to what has been described above, and that various modifications and changes may be made without departing from the scope thereof. The scope of the invention is limited only by the appended claims.
Claims (10)
1. A titanium-based lead dioxide electrode for degrading rhodamine B is characterized by comprising a titanium-based body layer, wherein a tin-antimony oxide bottom layer and Ce and SDBS codoped modified PbO are sequentially plated from the inside to the outside of the titanium-based body2And an active layer.
2. The preparation method of the titanium-based lead dioxide electrode for degrading rhodamine B according to claim 1, which is characterized by comprising the following steps:
1) pretreating a titanium substrate;
2) thermally depositing a tin-antimony oxide bottom layer;
3) electrodeposition of Ce, SDBS codoped modified PbO2Active layer: electrodepositing an active layer in a nitric acid system by taking a titanium substrate with a tin-antimony oxide coating subjected to thermal deposition as an anode and a titanium substrate as a cathode, wherein the nitric acid system contains Ce, SDBS, lead nitrate and copper nitrate; the current density of the electrodeposition is 100 to 300A/m2The electrodeposition temperature is 30-70 ℃, and the electrodeposition time is 1-4 h.
3. The preparation method of the titanium-based lead dioxide electrode for degrading rhodamine B as claimed in claim 2, wherein the step 1) of pretreatment of the titanium substrate specifically comprises the following steps:
firstly, cutting and sand blasting a titanium substrate, and removing surface oxide skin; and then ultrasonically removing oil in an ethanol solution for 10-20 min, etching the solution in a slightly boiling oxalic acid solution for 1-3 h, and washing the etched solution with deionized water for later use.
4. The preparation method of the titanium-based lead dioxide electrode for degrading rhodamine B as claimed in claim 3, wherein the concentration of the oxalic acid solution is 3% -10%.
5. The preparation method of the titanium-based lead dioxide electrode for degrading rhodamine B as claimed in claim 2, wherein the step 2) of thermally depositing the tin antimony oxide bottom layer specifically comprises the following steps:
2.1) dissolving tin tetrachloride and antimony trichloride in a mixed solution of concentrated hydrochloric acid and ethanol to prepare a coating solution, and coating the coating solution on the surface of the titanium substrate prepared in the step 1);
2.2) drying in a forced air drying oven at the temperature of 100-130 ℃ for 5-10 min;
2.3) repeating the steps 2.1) to 2.2) for 5-9 times, then placing the dried titanium matrix in a muffle furnace, sintering at the temperature of 400-550 ℃ for 50-70 min, taking out and naturally cooling to room temperature.
6. The preparation method of the titanium-based lead dioxide electrode for degrading rhodamine B according to claim 5, wherein the content of each component of the coating solution in the step 2.1) is 40-60 g/L concentrated hydrochloric acid, 450-600 g/L ethanol, 60-100 g/L stannic chloride and 20-40 g/L antimony trichloride.
7. The preparation method of the titanium-based lead dioxide electrode for degrading rhodamine B as claimed in claim 2, wherein the step 3) comprises the following steps:
preparing a mixed solution of lead nitrate and copper nitrate in an electrolytic bath, heating to 30-70 ℃, adding two doping agents Ce and SDBS, and uniformly stirring to form an acidic deposition solution; and then respectively fixing the titanium substrate anode and the titanium plate cathode of the hot-deposited tin-antimony oxide coating in an electrolytic bath, and electrifying and depositing for 1-4 h.
8. The preparation method of the titanium-based lead dioxide electrode for degrading rhodamine B as claimed in claim 7, wherein the acid precipitation is performedThe accumulated liquid is prepared by deionized water, wherein the accumulated liquid contains 100-150 g/L Pb2+，60～100g/L Cu2+，1～8mmol/L Ce3+And 1-40 mg/L SDBS.
9. The application of the titanium-based lead dioxide electrode for degrading rhodamine B in dye wastewater according to claim 1.
10. The use according to claim 9, characterized in that the dye waste water contains neutral red or methyl orange or rhodamine B.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112093858A (en) * | 2020-08-17 | 2020-12-18 | 浙江工业大学 | Preparation method and parameter design method of long-life lead dioxide electrode |
| CN112723490A (en) * | 2020-12-09 | 2021-04-30 | 苏州新能环境技术股份有限公司 | Carbon nanotube modified lead dioxide electrode and preparation method and application thereof |
| CN114016065A (en) * | 2021-10-27 | 2022-02-08 | 西安泰金工业电化学技术有限公司 | Preparation method of porous titanium-based lead dioxide electrode |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102701329A (en) * | 2012-07-17 | 2012-10-03 | 北京师范大学 | Preparation method of porous nanometer crystal electrodes and application of porous nanometer crystal electrodes |
| CN102897875A (en) * | 2012-10-24 | 2013-01-30 | 南京大学 | Cerium-doped lead dioxide electrode, and preparation method and application thereof in quick decolorization and efficient mineralization of basic dyes |
| CN105239094A (en) * | 2015-11-12 | 2016-01-13 | 南京信息职业技术学院 | Graphene-doped and lanthanum-modified titanium-based lead dioxide electrode and preparation method thereof |
| CN105776441A (en) * | 2016-03-11 | 2016-07-20 | 上海应用技术学院 | Three-dimensional porous titanium substrate lead dioxide electrode as well as preparation method and application thereof |
-
2019
- 2019-12-26 CN CN201911360884.0A patent/CN110980890A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102701329A (en) * | 2012-07-17 | 2012-10-03 | 北京师范大学 | Preparation method of porous nanometer crystal electrodes and application of porous nanometer crystal electrodes |
| CN102897875A (en) * | 2012-10-24 | 2013-01-30 | 南京大学 | Cerium-doped lead dioxide electrode, and preparation method and application thereof in quick decolorization and efficient mineralization of basic dyes |
| CN105239094A (en) * | 2015-11-12 | 2016-01-13 | 南京信息职业技术学院 | Graphene-doped and lanthanum-modified titanium-based lead dioxide electrode and preparation method thereof |
| CN105776441A (en) * | 2016-03-11 | 2016-07-20 | 上海应用技术学院 | Three-dimensional porous titanium substrate lead dioxide electrode as well as preparation method and application thereof |
Non-Patent Citations (5)
| Title |
|---|
| XIAOYUE DUAN ET AL.: "Fabrication of a hydrophobic SDBS-PbO2 anode for electrochemical degradation of nitrobenzene in aqueous solution", 《"FABRICATION OF A HYDROPHOBIC SDBS-PBO2 ANODE FOR ELECTROCHEMICAL DEGRADATION OF NITROBENZENE IN AQUEOUS SOLUTION"》 * |
| 周生刚等: "《金属基层状复合功能材料的研制与性能》", 31 May 2015 * |
| 杨卫华等: "稀土改性Ti/Sb-SnO_2/β-PbO_2电极的制备与性能", 《稀有金属材料与工程》 * |
| 陈步明等: "《有色金属电积用二氧化铅复合电极材料》", 28 February 2019 * |
| 陈野等: "Ti/SnO_2-Sb_2O_5/PbO_2电极的制备及降解不同污染物性能研究", 《环境科学学报》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112093858A (en) * | 2020-08-17 | 2020-12-18 | 浙江工业大学 | Preparation method and parameter design method of long-life lead dioxide electrode |
| CN112093858B (en) * | 2020-08-17 | 2022-11-04 | 浙江工业大学 | Preparation method and parameter design method of long-life lead dioxide electrode |
| CN112723490A (en) * | 2020-12-09 | 2021-04-30 | 苏州新能环境技术股份有限公司 | Carbon nanotube modified lead dioxide electrode and preparation method and application thereof |
| CN114016065A (en) * | 2021-10-27 | 2022-02-08 | 西安泰金工业电化学技术有限公司 | Preparation method of porous titanium-based lead dioxide electrode |
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