CN112093858B - Preparation method and parameter design method of long-life lead dioxide electrode - Google Patents
Preparation method and parameter design method of long-life lead dioxide electrode Download PDFInfo
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- 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
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- 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
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Abstract
The invention discloses a preparation method and an intelligent design method of a long-life lead dioxide electrode, and belongs to the technical field of electrochemistry. In the process of treating organic pollutants by the long-life lead dioxide anode, the stability of the anode is high, the service life is long, and the operating cost of the electrochemical technology can be reduced. The first long-life lead dioxide electrode provided by the invention comprises a lead dioxide surface active layer, a tin-antimony oxide intermediate layer and a titanium substrate, and a three-layer sandwich structure is formed and has surface active sites and redox sites. The second lead dioxide electrode with long service life provided by the invention has the advantages that the crystal grains are in a pyramid structure, the surface is compact, the specific surface area is large, and the adhesion between the surface active layer and the substrate is favorably improved. The long-life lead dioxide electrode provided by the invention can effectively block H 2 SO 4 The stability and the service life of the electrode are improved.
Description
Technical Field
The invention belongs to the technical field of electrochemistry. In particular to a lead dioxide electrode with high stability and long service life and an intelligent preparation method suitable for the design and performance regulation of the catalytic electrode.
Background
The catalytic electrode realizes the degradation of organic matters by generating high-activity hydroxyl free radicals (. OH) in situ under the action of an external electric field. Because the electrochemical reaction only needs to carry out electron transfer between the wastewater and the electrode, no redundant reaction and secondary pollution exist, various pollutants can be effectively removed, and valuable metal ions and other byproducts in the wastewater can be recovered. In the field of organic wastewater degradation, noble metal electrodes such as platinum, aluminum, BDD and the like have good catalytic activity. However, the noble metal catalyst has high cost and limited resources, and cannot be used on a large scale, so that the noble metal electrode does not meet the requirements of industrial application in terms of cost and service life. PbO 2 The electrode has the advantages of good corrosion resistance, strong oxidation resistance, low cost and the like, but the lead dioxide active layer can not be stably attached to the substrate in the actual use process. This is because the nascent oxygen generated on the surface of the electrode partially penetrates through the surface active layer and then penetrates into the Ti radicalA body and react therewith to form TiO 2 Passivation films, which seriously affect the electrode conductivity and cause the surface active layer to peel off. In addition, the surface active layer of the electrode can generate a polymeric film in the degradation process, so that the electrode is subjected to a poisoning and inactivation phenomenon. Thus, pbO is applied on an industrial scale 2 The key point of the electrode lies in developing a lead dioxide electrode which can solve the problems and has strong adhesiveness, high stability and long service life.
Is commonly used for preparing PbO at present 2 The electrode method is an electrodeposition method, which refers to an electric crystallization process that metal ions in a solution obtain electrons on an electrode, the electrons are reduced into metal atoms, and then monoatomic ions are adsorbed on the surface of the electrode to combine into crystals. Common electrode modification methods are achieved by adding various ions to the deposition solution or changing the electrodeposition conditions. Because the process conditions in the electrode preparation process are complex, the process conditions and various factors influencing the final performance of the electrode are difficult to regularly summarize and systematically know, so the current optimal electrode preparation conditions are limited to the prior experience summarization.
Patent application No. 202010087985.1, title Ti/Sb-SnO 2 /PVDF-CNT-PbO 2 An electrode and a method for preparing the same. It provides a novel PbO 2 The electrode and the preparation method thereof realize that the carbon nano tube and the polyvinylidene fluoride are in PbO by adding the carbon nano tube and the polyvinylidene fluoride into the electroplating solution 2 And co-doping in the active layer improves the catalytic activity and the service life of the electrode. Because the preparation method only compares the electrode performance change of the electrode before and after the doping of the additive, and the actual preparation process also has multiple factors such as current density, pH value, temperature and the like, whether the method is suitable for various process conditions still needs to be further demonstrated.
Patent application No. 201410279964.4, patent name porous nanocrystalline Ti/SnO 2 -Sn/Ce-PbO 2 A method for preparing an electrode. Aiming at the pollution condition of the perfluorooctanoic acid, the invention provides a novel purification technology capable of efficiently mineralizing the perfluorooctanoic acid in water under mild conditions, and in addition, the invention also provides a novel porous nanocrystalline PbO 2 A method for producing the electrode, however, the methodDetailed data in the preparation process may be established on the basis of experience of operators or limited single-factor experiments, and influences of solution concentration of polyethylene glycol, ce addition amount, matrix pretreatment, electrode roasting temperature and the like related to the preparation process on electrode performance and corresponding optimization schemes are not fully considered.
Disclosure of Invention
The first purpose of the invention is to provide a preparation method of a lead dioxide electrode with high stability and long service life.
According to the preparation method of the long-life lead dioxide electrode, disclosed by the invention, an electrodeposition method is adopted, and the surface crystal structure of the obtained lead dioxide electrode is a compact pyramid type, so that the lead dioxide electrode can effectively and durably resist corrosion. Pb (NO) in deposition solution for electrodeposition method 3 ) 2 The concentration is 0.5mol/L, the NaF concentration is 0.05mol/L, and HNO in the sediment liquid 3 The concentration is 1.0mol/L, and the current density of electrodeposition is 40mA/cm 2 The deposition temperature for electrodeposition was 65 ℃ and the pH for electrodeposition was 1.4.
Preferably, the obtained lead dioxide electrode is particularly Ti/Sb-SnO 2 /PbO 2 And an electrode.
Preferably, the lead dioxide surface active layer adopts alpha-PbO 2 、β-PbO 2 、Pb 3 O 4 And PbO.
Preferably, the substrate of the lead dioxide electrode is a metallic titanium substrate.
Preferably, the intermediate layer of the lead dioxide electrode is a tin antimony oxide intermediate layer.
The second purpose of the invention is to provide an optimization method for parameter design and performance regulation and control for the lead dioxide preparation method.
The parameter design method in the preparation process of the long-life lead dioxide electrode comprises the following steps:
step one, adding Pb (NO) 3 ) 2 Concentration, naF concentration, HNO 3 The concentration, the current density, the deposition temperature and the pH value are taken as six key parameters, and a cell deposition method preparation II is established through a Box-Behnken design methodPreparing n basic electrodes of the lead oxide electrode; six key parameters in the preparation schemes of the n basic electrodes are not completely the same, and n is more than or equal to 30 and less than or equal to 60.
Step two, preparing n lead dioxide electrodes by using n basic electrode preparation schemes respectively, and testing the service life of the prepared n lead dioxide electrodes respectively; and establishing a basic experiment data set consisting of n basic electrode preparation schemes and corresponding service lives.
Step three, establishing a Generalized Regression Neural Network (GRNN) by taking six key parameters as input variables and taking the service life as an output variable; adjusting parameters of the generalized regression neural network according to the basic experiment data set; and (3) predicting the service life of the prepared lead dioxide electrode by the generalized regression neural network according to the six input key parameters.
Step four, constructing a virtual electrode space through a Genetic Algorithm (GA) and a generalized recurrent neural network; the virtual electrode space comprises service lives corresponding to various different pairs of key parameter combinations; and searching the virtual electrode space by taking the service life maximization as an optimization target to obtain the numerical values of the six key parameters corresponding to the lead dioxide electrode with the maximum service life. And preparing the lead dioxide electrode with the pyramid type crystal structure according to the six key parameters.
Preferably, in step three, the generalized recurrent neural network is established in the Matlab platform.
Preferably, in the third step, the generalized regression neural network has a four-layer network structure and includes an input layer, a mode layer, a summation layer and an output layer; the number of neurons in the input layer is equal to the input vector dimension 6, the number of neurons in the mode layer is equal to the number n of learning samples, the summation layer adopts weighting operation, and the variable of the output layer is 1.
Preferably, the parameters of the generalized regression neural network in step three include smoothing parameters of radial basis functions, and the optimized values are obtained by a cross-validation method.
Preferably, in step four, search region boundaries, iteration times and population numbers are set in the genetic algorithm.
The invention has the beneficial effects that:
1. according to the invention, six key parameters in the preparation process of the lead dioxide electrode are selected and optimized to obtain the compact and compact pyramid Ti/Sb-SnO with the surface structure 2 /PbO 2 The electrode material can effectively inhibit the immersion of sulfuric acid, thereby improving the stability and the service life of the lead dioxide electrode.
2. The invention can synchronously have a nano-scale crystal particle structure with larger specific surface area, is beneficial to improving the adhesive force between the surface active layer and the matrix, greatly improves the integral catalytic activity of the electrode, and can meet the degradation requirements of different types of wastewater.
3. The design of the invention can complete modeling and prediction only by a small amount of basic experiments (30-60 groups), thereby reducing the material development cost and shortening the material research and development and test period.
4. The intelligent preparation method of the electrode material provided by the invention has universality and can be used for rapidly optimizing and screening other catalytic electrode materials influenced by multiple preparation parameters.
Drawings
FIG. 1 is an electron micrograph of the surface of a lead dioxide electrode prepared in example 1 of the present invention (the surface can be seen to be pyramidal);
fig. 2 is a graph comparing the accelerated life test results of the lead dioxide electrodes obtained in example 1 of the present invention and the prior art.
FIG. 3 is a cyclic voltammetric scan of a lead dioxide electrode prepared in example 1 of the present invention;
fig. 4 is a logic diagram of the parameter design method according to embodiment 2 of the present invention.
Detailed Description
The invention is further described below with reference to the accompanying drawings.
Example 1
As shown in figure 1, the preparation method of the long-life lead dioxide electrode adopts an electrodeposition method, and the obtained lead dioxide electrode is particularly Ti/Sb-SnO 2 /PbO 2 Electrode, crystal structure is compact pyramid type, canCan effectively and durably resist corrosion. The substrate of the obtained lead dioxide electrode adopts a metallic titanium substrate, the intermediate layer adopts a tin-antimony oxide intermediate layer, and the surface active layer adopts alpha-PbO 2 、β-PbO 2 、Pb 3 O 4 And PbO.
Pb (NO) in deposition solution for electrodeposition method 3 ) 2 The concentration is 0.5mol/L, the NaF concentration is 0.05mol/L, and HNO in the sediment liquid 3 The concentration is 1.0mol/L, and the current density of electrodeposition is 40mA/cm 2 The deposition temperature for electrodeposition was 65 ℃ and the pH for electrodeposition was 1.4.
The lead dioxide electrode with the thickness of 29 μm prepared according to the preparation method is loaded on a metallic titanium base. To test the useful life of the electrode, accelerated life tests were used for characterization. Wherein the electrode to be detected is used as an anode, the stainless steel sheet is used as a cathode, the silver-silver chloride electrode is used as a reference electrode, the electrolyte is 2mol/L sulfuric acid solution, the temperature is 60 ℃, and the current density is 1A/cm 2 Under the conditions of (a). When the anode potential was 5V higher than the initial potential, the electrode was judged to be deactivated. The result shows that the beta-PbO in the lead dioxide electrode prepared by the invention 2 The proportion is high, and the crystal grains on the surface of the electrode active layer are tightly piled up to be pyramid-shaped, and the whole body is flat and compact. Through accelerated life test, the optimal lead dioxide catalytic electrode material is relatively stable, and the lead dioxide catalytic electrode material is prepared in a 2mol/L sulfuric acid solution at the temperature of 60 ℃ and the current density of 1A/cm 2 Under the condition (1), the anode potential is sharply increased only after the electrolysis time is more than or equal to 150 hours.
On the basis, two comparison groups are introduced to further verify the technical effect of the lead dioxide prepared by the invention as follows:
Ti/Sb-SnO prepared by Using this example 2 /PbO 2 As experimental groups; ti/Sb-SnO prepared by prior art 2 /PbO 2 As a first control group, ti/Sb-SnO doped with a metal element such as Ce or Bi was used 2 /M-PbO 2 The electrode material is used as a second control group; the electrodes in the experimental group, the first control group and the second control group are all loaded on a titanium substrate with a uniform specification, and the quality, the area and the distance of the electrodes are equal.
The test conditions were: the service life of the electrode was tested by accelerated life testing. Wherein the electrode to be detected is taken as an anode, the stainless steel sheet is taken as a cathode, the silver-silver chloride electrode is taken as a reference electrode, the electrolyte is 2mol/L sulfuric acid solution, the temperature is 60 ℃, and the current density is 1A/cm 2 Under the conditions of (1). When the anode potential was higher than the initial potential by 5V, the electrode was considered to be deactivated.
For the first control group, existing electrodeposition techniques were used to prepare Ti/Sb-SnO 2 /PbO 2 When the electrode is used, the current density, pH value and Pb of the deposit are required to be adjusted 2+ Multiple comparison tests and electrode performance tests are performed on multiple process parameters such as concentration to determine the optimal deposition conditions. Although the prepared electrode can meet the catalytic activity required by degrading organic matters, higher stability is difficult to obtain at the same time, so that the comprehensive utilization rate of the electrode has a space for improvement.
For the second control group, ti/Sb-SnO doped with metal elements such as Ce, bi and the like 2 /M-PbO 2 The electrode can be prepared into porous nano-crystalline grains only under the conditions of low pH value and high current density, and the doped metal elements can form overlapped hemispherical grains in the angle crystals. Although such a hemispherical structure is advantageous for oxidation of organic substances, stability of the material is reduced, and the service life of the electrode is shortened. As shown in FIG. 2, the Ti/Sb-SnO prepared in this example can be seen by comparing the accelerated life tests 2 /PbO 2 The electrode (the inverted triangle connecting line) is relatively stable, when the electrolysis time reaches 150h, the anode potential rises rapidly, and the electrode is inactivated after 162 h; the service life of the lead dioxide electrode (regular triangle connecting line) and the Bi-doped lead dioxide electrode (round dot connecting line) prepared by the prior art is relatively short, and the anode potential continuously rises and then is inactivated within 100 hours.
For the experimental group, the intelligently prepared high-service-life lead dioxide electrode Ti/Sb-SnO related to the embodiment 2 /PbO 2 The method can realize maximization of the service life of the electrode while giving consideration to the catalytic activity of the electrode, greatly improve the stability of the catalytic electrode in practical industrial application, and reduce the operation cost for the application of electrochemical oxidation. Therefore, the catalytic electrode material for degrading organic matters related to the embodiment is compared with the prior catalytic electrode materialSome catalysts have better electrode stability and comprehensive benefits, and can effectively prolong the service life of the lead dioxide electrode.
To test the stability of the lead dioxide electrode described in this example, ti/Sb-SnO was tested 2 /PbO 2 The electrode was subjected to cyclic voltammetric scanning in an electrolyte containing 0.2mol/L NaSO4 and 0.1mol/L HCl, continuously scanned 200 times from 0 to 2.0V, at a scanning rate of 10mV/s. As shown in fig. 3, the high current at the electrode was 5.7mA in the first cycle. After 100 consecutive cycles, the high current dropped to 5.6mA, maintaining 98% of the original value. After 200 consecutive cycles, the high current still maintained 97% of the original value. The continuous scanning result shows that the electrode has excellent relative stability.
In order to evaluate the safety of the lead dioxide electrode in the embodiment, the lead dioxide electrode is characterized by the precipitation amount of lead ions after the lead dioxide electrode is degraded in wastewater. Taking an electrode to be detected as a working electrode, a platinum sheet electrode as an auxiliary electrode and a calomel electrode as a reference electrode, carrying out electrocatalytic oxidation in 0.5mol/L Na2SO4 electrolyte containing 50mg/L aniline for 2.5h, and detecting Pb by using ICP-MS (inductively coupled plasma mass spectrometer) 2+ And (4) content. The results show that Pb dissolved from the electrode surface 2+ About 0.008mg/L, which is lower than the standard of drinking water (less than or equal to 0.01 mg/L). This indicates that the electrode not only has a long life but also has excellent stability and safety.
Example 2
As shown in fig. 4, a parameter design method in the preparation process of a lead dioxide electrode with a long service life is obtained by researching the composition of a lead dioxide electrodeposition plating solution, the temperature in the preparation process, the relationship between the pH value of the plating solution and the service life of a material based on a generalized regression neural network and a genetic algorithm optimization machine learning framework (GRNN-GA), and developing and screening the relationship, wherein the specific design method comprises the following steps:
step one, designing an experiment by a Box-Behnken design method (BBD) in a Response surface analysis (RSM) method, and using Pb (NO) 3 ) 2 Concentration, naF concentration, HNO 3 The concentration, the current density, the deposition temperature and the pH value are taken as key parameters, and n basic electrode preparation schemes are formulated(ii) a The six key parameters in the n base electrode preparation protocols are not exactly the same. N is more than or equal to 30 and less than or equal to 60.
And step two, respectively preparing n lead dioxide electrodes according to n basic electrode preparation schemes obtained by a Box-Behnken design method (namely preparing the lead dioxide electrodes by an electrodeposition method according to the Pb (NO 3) 2 concentration, the NaF concentration, the HNO3 concentration, the current density, the deposition temperature and the pH value set by the basic electrode preparation schemes), and respectively carrying out performance tests on the prepared n lead dioxide electrodes to obtain the service lives of the n electrodes, thereby establishing a basic experiment data set consisting of the n basic electrode preparation schemes and the corresponding service lives thereof.
Step three, establishing a Generalized Regression Neural Network (GRNN) on a Matlab platform by taking six key parameters as input variables and taking the service life as output variables; and obtaining the smooth parameters of the optimized radial basis function by a cross verification method to ensure that the smooth parameters reach the expected prediction precision. After the parameters are adjusted, any six key parameters are input into the generalized regression neural network, and the service life of the lead dioxide electrode corresponding to the six key parameters can be predicted.
And step four, adopting a Genetic Algorithm (GA) in a Matlab optimization tool box, establishing a virtual electrode space by setting parameters of the Genetic algorithm including search area boundaries, iteration times and population quantity and combining a generalized regression neural network, and searching the virtual electrode space by taking service life maximization as an optimization target to obtain values of six key parameters corresponding to the lead dioxide electrode with the maximum service life. The six key parameters obtained were as follows: pb (NO) 3 ) 2 The concentration is 0.5mol/L, the NaF concentration is 0.05mol/L, and HNO in the sediment liquid 3 The concentration is 1.0mol/L, and the current density of electrodeposition is 40mA/cm 2 The deposition temperature for electrodeposition was 65 ℃ and the pH for electrodeposition was 1.4.
The embodiment provides a feasible strategy for developing the electrode material with high stability and long service life influenced by multiple parameters by accurately regulating and controlling six key variables in the preparation process of the lead dioxide electrode. This strategy is achieved in this embodiment byFor Pb in the deposition liquid 2+ The regulation and control of the lead ion lead-free anode material avoid the phenomena of reduced crystallinity and reduced conductivity of the electrode caused by excessive lead ions, and also ensure that the problem of reduced catalytic activity of the electrode material caused by the reduction of active components is avoided; the pH value is accurately controlled by regulating and controlling nitric acid, so that the thermodynamic growth of the lead dioxide electrode is always in an optimal area, and the accurate control of the composition of the prepared lead dioxide phase is facilitated; by regulating and controlling the deposition current density, the finally obtained lead dioxide surface active layer crystal grains are ensured to be mainly in an expected pyramid shape on the microstructure, an active layer with a compact and flat structure is obtained, the condition that an acid solution permeates into an electrode and the surface active layer falls off is delayed, and the stability and the service life of the lead dioxide catalytic electrode are enhanced; according to the intelligent preparation method, under the condition that the variables are continuously and nonlinearly changed, a method capable of coordinating the key variables is found, so that the prepared lead dioxide electrode is close to or reaches the balance point of the maximum service life of the lead dioxide electrode.
Claims (7)
1. A preparation method of a long-life lead dioxide electrode is characterized by comprising the following steps: the prepared long-life lead dioxide electrode comprises a lead dioxide surface active layer, a tin-antimony oxide intermediate layer and a titanium substrate, and a three-layer sandwich structure is formed and has surface active sites and redox sites; the surface active layer of the lead dioxide adopts beta-PbO 2 (ii) a The lead dioxide surface active layer is formed by electrodeposition; the parameters of electrodeposition were as follows: pb (NO) in the deposition solution 3 ) 2 The concentration is 0.5mol/L, the NaF concentration is 0.05mol/L, and HNO in the sediment liquid 3 The concentration is 1.0mol/L, and the current density of electrodeposition is 40mA/cm 2 The deposition temperature of the electrodeposition is 65 ℃, and the pH value of the electrodeposition is 1.4;
the various parameters of electrodeposition were determined by the following procedure:
step one, designing an experiment by a Box-Behnken design method, and using Pb (NO) 3 ) 2 Concentration, naF concentration, HNO 3 The concentration, the current density, the deposition temperature and the pH value are used as six key parameters to formulate n groups of basic catalyst preparation methodsN is more than or equal to 30 and less than or equal to 60;
respectively carrying out electrolytic preparation according to a basic electrode preparation scheme given by a Box-Behnken design method, and respectively carrying out performance test on the n prepared electrodes to obtain a basic experiment data set consisting of six key parameters of the n electrodes and the corresponding service lives of the n electrodes;
step three, establishing a generalized regression neural network by taking six key parameters as input variables and taking the service life as an output variable; obtaining the relation between six key parameters and the service life through a generalized regression neural network;
and step four, adopting a genetic algorithm to construct a virtual electrode space, taking the maximum service life as an optimization target, and searching the virtual electrode space to obtain the values of six key parameters corresponding to the maximum service life.
2. The production method according to claim 1, characterized in that: the electrodes are in a pyramid structure which is tightly stacked and can effectively block H 2 SO 4 The stability and the service life of the electrode are improved.
3. The method of claim 1, wherein: the substrate adopts a TA2 metal titanium sheet, the size is 1cm multiplied by 1cm, and the thickness is 1mm.
4. The production method according to claim 3, characterized in that: the metal titanium substrate is subjected to sand paper polishing, naOH alkaline cleaning and oxalic acid etching in advance to form a uniform pitted surface, so that the binding force between the titanium substrate and the metal oxide film layer is enhanced.
5. The production method according to claim 1 or 2, characterized in that: the intermediate layer is a tin-antimony oxide intermediate layer.
6. The method of claim 1, wherein: in the third step, the generalized regression neural network is a four-layer network structure and comprises an input layer, a mode layer, a summation layer and an output layer; the number of neurons in the input layer is equal to the input vector dimension 6, the number of neurons in the mode layer is equal to the number n of learning samples, the summation layer adopts weighting operation, and the variable of the output layer is 1.
7. The method of claim 1, wherein: in the third step, the generalized recurrent neural network is established in a Matlab platform; parameters of the generalized regression neural network comprise smooth parameters of a radial basis function, and an optimized value of the parameters is obtained by a cross validation method; in the fourth step, search area boundaries, iteration times and population quantity are set in the genetic algorithm.
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2012251195A (en) * | 2011-06-02 | 2012-12-20 | Japan Carlit Co Ltd:The | Electrode for use in electrolysis, and method of producing the same |
| 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 |
| CN105621541A (en) * | 2015-12-31 | 2016-06-01 | 浙江工业大学 | Transition-metal doped lead dioxide electrode for wastewater treatment as well as preparation method and application thereof |
| CN106277216A (en) * | 2016-08-05 | 2017-01-04 | 浙江工业大学 | Indium doping ti-supported lead dioxide electric pole and its preparation method and application |
| CN108217852A (en) * | 2018-01-11 | 2018-06-29 | 重庆大学 | High life, high catalytic activity lead dioxide electrode |
| CN110980890A (en) * | 2019-12-26 | 2020-04-10 | 西安泰金工业电化学技术有限公司 | Titanium-based lead dioxide electrode for degrading rhodamine B and preparation method and application thereof |
-
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Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2012251195A (en) * | 2011-06-02 | 2012-12-20 | Japan Carlit Co Ltd:The | Electrode for use in electrolysis, and method of producing the same |
| 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 |
| CN105621541A (en) * | 2015-12-31 | 2016-06-01 | 浙江工业大学 | Transition-metal doped lead dioxide electrode for wastewater treatment as well as preparation method and application thereof |
| CN106277216A (en) * | 2016-08-05 | 2017-01-04 | 浙江工业大学 | Indium doping ti-supported lead dioxide electric pole and its preparation method and application |
| CN108217852A (en) * | 2018-01-11 | 2018-06-29 | 重庆大学 | High life, high catalytic activity lead dioxide electrode |
| CN110980890A (en) * | 2019-12-26 | 2020-04-10 | 西安泰金工业电化学技术有限公司 | Titanium-based lead dioxide electrode for degrading rhodamine B and preparation method and application thereof |
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