CN103508517A - Carbon nanotube modified titanium based fluorine-containing lead dioxide electrode and preparation method thereof - Google Patents
Carbon nanotube modified titanium based fluorine-containing lead dioxide electrode and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a carbon nanotube modified titanium based fluorine-containing lead dioxide electrode and a preparation method thereof. The carbon nanotube modified titanium based fluorine-containing lead dioxide electrode is prepared by: taking a titanium plate as a substrate, polishing and etching the titanium plate substrate, performing thermal deposition of a tin antimony oxide base layer, then conducting electrodeposition of an alpha-PbO2 intermediate layer in an alkaline plating solution, and finally performing electrodeposition of a beta-PbO2 active layer in an acidic plating solution containing fluoride ions, a surfactant and a carbon nanotube. Compared with ordinary titanium based fluorine-containing lead dioxide electrodes, the carbon nanotube modified titanium based fluorine-containing lead dioxide electrode has high catalytic activity and long service life. The electrode can be used as an anode to treat organic wastewater, can achieve a good degradation effect, and can realize mineralization on poisonous and harmful organic matters that are difficult to degrade. Being easy and convenient to operate, the electrode provided by the invention is a potential electrode suitable for water treatment.
Description
Technical field
The present invention relates to a kind of carbon nano tube modified titanium base Lead dioxide anode modifiedby fluorine resin and preparation method thereof, and use it for catalytic oxidation and remove organic pollutants, belong to water technology and electrochemical field.
Background technology
In recent years, By Electrocatalytic Oxidation does not consume or seldom consumes chemical reagent because having advantages of, do not bring secondary pollution, operation is controlled easily, can mineralising refractory organic etc. additive method hardly match, become the study hotspot of water technology.But also exist the current efficiency of electrode low at present, electrode life the short or electrode shortcoming such as involve great expense.Therefore how to prepare and there is high current efficiency, high stability, and cheap electrode is a major issue of this area research.
Lead dioxide electrode is to study one of electrode materials comparatively widely, has the features such as good conductivity, solidity to corrosion is strong, cost is low, preparation method is simple, oxygen evolution potential is higher, oxidation capacity is stronger.But because lead dioxide electrode has in use less stable, settled layer is easy to peel off, and the not high enough shortcoming of current efficiency.In recent years, a large amount of scholars is devoted to lead dioxide electrode to carry out effective modification, to improve current efficiency and the stability of lead dioxide electrode.For example patent CN101054684A provides a kind of preparation method of Lead dioxide anode modifiedby fluorine resin, and its lead dioxide electrode making has advantages of that coating internal stress is little, bonding force good and electrode life is long; Patent CN101417831 proposes the titanium base Lead dioxide anode modifiedby fluorine resin of a kind of high absorption property particle (as Powdered Activated Carbon or chitosan) and a kind of active metal (as bismuth, nickel, lanthanum, cerium, erbium) modification, and it has advantages of, and electrode cost is lower, oxidation organic pollutants activity is higher, internal stress is little and electrode life is long.
Carbon nanotube is as monodimension nanometer material, lightweight, and hexagonal structure connects perfect, has many abnormal mechanics, electricity and chemical property.Its wide application prospect of going deep into along with carbon nanotube and nano materials research also constantly showed in recent years.For this reason, we propose carbon nanotube to be doped under the effect of tensio-active agent in the top layer of titanium base Lead dioxide anode modifiedby fluorine resin, to improve the catalytic oxidation activity of electrode and the work-ing life of electrode.
Summary of the invention
The object of this invention is to provide a kind of carbon nano tube modified titanium base Lead dioxide anode modifiedby fluorine resin and preparation method thereof, this electrode is under the effect of tensio-active agent, carbon nanotube (single wall or many walls) to be doped in the surfactivity layer of Lead dioxide anode modifiedby fluorine resin, and the carbon nano tube modified titanium base Lead dioxide anode modifiedby fluorine resin cost that makes is low, activity is high, the life-span is long.
The object of the present invention is achieved like this, and this carbon nano tube modified titanium base Lead dioxide anode modifiedby fluorine resin comprises:
Titanium board substrate;
The tin-antimony oxide bottom of heat deposition on titanium board substrate;
α-the PbO of galvanic deposit on tin-antimony oxide bottom
2middle layer;
Under Action of Surfactant, galvanic deposit is at α-PbO
2carbon nano tube modified fluorine-containing β-PbO on middle layer
2surfactivity layer.
The preparation method of carbon nano tube modified titanium base Lead dioxide anode modifiedby fluorine resin comprises the following steps:
1., the pre-treatment of titanium matrix: first with 120 order flint papers polishing titanium board substrates, then polish to titanium board substrate and present silvery white metalluster with 600 orders and 1200 object fine sandpapers successively, with deionized water rinsing; The titanium board substrate of polishing is placed in to acetone supersound process 5 ~ 10 minutes, wipe oil; Again the titanium board substrate after acetone supersound process is placed in to deionized water for ultrasonic and processes 5 ~ 10 minutes, remove acetone and other impurity; Then the titanium board substrate after deionized water for ultrasonic is processed is immersed in oxalic acid etching liquid under 80 degrees Celsius ~ micro-condition of boiling to etching 1 ~ 4 hour, after taking-up, the titanium board substrate after etching is placed in to oxalic acid and preserves liquid and preserve.
Described oxalic acid etching liquid is that 87 ~ 176 grams of oxalic acid are dissolved in 1 liter of deionized water formulated; It is that 10 grams of oxalic acid are dissolved in 1 liter of deionized water formulated that described oxalic acid is preserved liquid.
2., the preparation of tin-antimony oxide bottom: tin trichloride and four antimony chlorides are dissolved in concentrated hydrochloric acid and isopropyl alcohol mixture and make coating liquid, on titanium board substrate surface after processing during 1. coating liquid is coated on, in electrically heated drying cabinet, under 120 degrees Celsius, dry 10 minutes, again the titanium board substrate of oven dry is placed in to 500 degrees Celsius of lower roastings of retort furnace 10 minutes, so repeat 5 to 10 times, last roasting time in retort furnace is 1 hour, naturally cools to room temperature.
3., α-PbO
2the preparation in middle layer: the titanium board substrate with tin-antimony oxide bottom that 2. step is prepared is as anode, the stainless steel plate of homalographic is as negative electrode, galvanic deposit α-PbO in being dissolved with the sodium hydroxide solution of PbO
2middle layer, the current density of galvanic deposit is 1 ~ 5mA/cm
2, depositing temperature is 30 ~ 60 degrees Celsius, depositing time is 0.5 ~ 2 hour.
4., carbon nano tube modified fluorine-containing β-PbO
2the preparation of surfactivity layer: step is made in 3. with α-PbO
2the titanium board substrate in middle layer is as anode, the stainless steel plate of homalographic is as negative electrode, the carbon nano tube modified fluorine-containing β-PbO of galvanic deposit in the fluorine-containing lead nitrate solution of the acidity that is mixed with carbon nanotube and tensio-active agent (as Sodium dodecylbenzene sulfonate, sodium laurylsulfonate or cetyl trimethylammonium bromide)
2surfactivity layer, the current density of galvanic deposit is 5 ~ 30mA/cm
2, depositing temperature is 45 ~ 85 degrees Celsius, depositing time is 0.5 ~ 2 hour.
The coating liquid of step described in is 2. to be that 10 ~ 15 milliliters of 37% concentrated hydrochloric acids, 50 ~ 100 milliliters of Virahols are formulated by 15 ~ 25 grams of tin tetrachloride, 1 ~ 5 gram of butter of antimony, mass concentration.
Step 3. described in galvanic deposit α-PbO
2the solution composition in middle layer is 0.05 ~ 0.12 mol/L PbO, 3.0 ~ 4.0 mol/L sodium hydroxide.
The galvanic deposit carbon nano tube modified fluorine-containing β-PbO of step described in 4.
2the solution composition of surfactivity layer is lead nitrate 0.4 ~ 0.6 mol/L, nitric acid 0.09 ~ 1.1 mol/L, Sodium Fluoride 0.01 ~ 0.06 mol/L, tensio-active agent (as Sodium dodecylbenzene sulfonate, sodium laurylsulfonate or cetyl trimethylammonium bromide) 0.05 ~ 5 grams per liter, carbon nanotube 0.5 ~ 20 grams per liter.
The present invention has following features:
(1) the prepared carbon nano tube modified titanium base Lead dioxide anode modifiedby fluorine resin of the present invention is usingd titanium plate as matrix, and tin-antimony oxide layer is bottom, α-PbO
2settled layer is middle layer, the fluorine-containing β-PbO of doped carbon nanometer pipe under Action of Surfactant
2settled layer is surfactivity layer.
(2) the present invention is by the doping of carbon nanotube, electro catalytic activity and the electroconductibility of electrode have been improved, adopt the prepared carbon nano tube modified titanium base Lead dioxide anode modifiedby fluorine resin By Electro-catalytic Oxidation Process para-chlorophenol of the present invention, in solution, total organic Carbon removal can reach 1.57 times of common titanium base Lead dioxide anode modifiedby fluorine resin.
(3) can reach 1.87 times of common titanium base Lead dioxide anode modifiedby fluorine resins the work-ing life of the prepared carbon nano tube modified titanium base Lead dioxide anode modifiedby fluorine resin of the present invention.
Accompanying drawing explanation
Fig. 1 is the structural representation of carbon nano tube modified titanium base Lead dioxide anode modifiedby fluorine resin of the present invention.
Fig. 2 is the scanning electron microscope (SEM) photograph of common titanium base Lead dioxide anode modifiedby fluorine resin.
Fig. 3 is the scanning electron microscope (SEM) photograph of the carbon nano tube modified titanium base Lead dioxide anode modifiedby fluorine resin of preparing under Sodium dodecylbenzene sulfonate effect of the present invention, and in figure, (a) magnification is 200 times, and (b) magnification is 1000 times.
Fig. 4 is the scanning electron microscope (SEM) photograph of the carbon nano tube modified titanium base Lead dioxide anode modifiedby fluorine resin of preparing under cetyl trimethylammonium bromide effect of the present invention, and in figure, (a) magnification is 200 times, and (b) magnification is 1000 times.
Embodiment
For the ease of the comparison of product of the present invention, we have prepared common titanium base Lead dioxide anode modifiedby fluorine resin, and concrete preparation method is as follows:
First with 120 order flint papers polishings titanium board substrates (30 millimeters * 50 millimeters * 0.8 millimeter), then with 600 orders and 1200 object fine sandpapers, polish to titanium board substrate and present silvery white metalluster successively, with deionized water rinsing; The titanium board substrate of polishing is placed in to acetone supersound process 10 minutes, wipe oil; Again the titanium board substrate after acetone supersound process is placed in to deionized water for ultrasonic and processes 10 minutes, remove acetone and other impurity; Then the titanium board substrate after deionized water for ultrasonic is processed is immersed in oxalic acid etching liquid to (oxalic acid etching liquid is that 150 grams of oxalic acid are dissolved in 1 liter of deionized water formulated) 85 degrees Celsius of lower etchings 2 hours, takes out and be placed on oxalic acid and preserve in liquid (it is that 10 grams of oxalic acid are dissolved in 1 liter of deionized water formulated that oxalic acid is preserved liquid) and preserve.Tin trichloride and four antimony chlorides are dissolved in and in concentrated hydrochloric acid and isopropyl alcohol mixture, make coating liquid (20 grams of SnCl
4, 2.0 grams of SgCl
3, 13 milliliters of mass concentrations are 37% concentrated hydrochloric acid, 87 milliliters of Virahols), by being kept at oxalic acid, preserve the titanium board substrate taking-up in liquid, utilize washed with de-ionized water surface, coating liquid is coated on clean titanium board substrate, in electrically heated drying cabinet, under 120 degrees Celsius, dry 10 minutes, again the titanium board substrate after drying is placed in to 500 degrees Celsius of lower roastings of retort furnace 10 minutes, so repeat 8 times, last roasting time in retort furnace is 1 hour, naturally cool to room temperature, obtain the titanium board substrate with tin-antimony oxide bottom.Using the titanium board substrate with tin-antimony oxide bottom as anode, using the stainless steel plate of homalographic as negative electrode, galvanic deposit α-PbO in 100 milliliters of electrodeposit liquids that are dissolved with 0.1 mol/L PbO and 3.5 mol/L sodium hydroxide
2middle layer, the current density of galvanic deposit is 3mA/cm
2, depositing temperature is 40 degrees Celsius, depositing time is 1 hour.After cleaning with deionized water, obtain with α-PbO
2the titanium board substrate in middle layer.Will be with α-PbO
2the titanium board substrate in middle layer is as anode, and the stainless steel plate of homalographic is as negative electrode, galvanic deposit β-PbO in 100 milliliters of mixing solutionss that contain 0.5 mol/L lead nitrate, 0.05 mol/L Sodium Fluoride and 1 mol/L nitric acid
2surfactivity layer, galvanic deposit current density is 15mA/cm
2, depositing temperature is 65 degrees Celsius, and depositing time is 1 hour, and the common titanium base Lead dioxide anode modifiedby fluorine resin that obtains preparing, as accompanying drawing 2.
Adopt this electrode as anode, the stainless steel plate of homalographic is as negative electrode, interpole gap is 1 centimetre, para-chlorophenol in catalytic oxidation water, the concentration of para-chlorophenol is 50 mg/litre, the sodium sulfate of 0.05 mol/L is done supporting electrolyte, and the volume of solution is 200 milliliters, and catalytic oxidation current density is 30mA/cm
2, temperature is 30 degrees Celsius, the clearance that reacts para-chlorophenol after 120 minutes is 78.47%, reacts after 180 minutes total organic Carbon removal in solution and can reach 56.57%.Adopting this electrode is that anode carries out accelerated life test, and in the sulphuric acid soln of 1 mol/L, temperature is under 60 degrees Celsius, 1A/cm
2current density under the weightlessness of 20 hours rear electrodes of electrolysis be 10.1mg/cm
2.
the specific embodiment of preparation product of the present invention is as follows:
Embodiment 1:
As shown in Figure 1: the structure of the titanium base Lead dioxide anode modifiedby fluorine resin that the present invention is carbon nano tube modified comprises:
Titanium board substrate 1;
The tin-antimony oxide bottom 2 of heat deposition on titanium board substrate;
α-the PbO of galvanic deposit on tin-antimony oxide bottom 2
2middle layer 3;
Under Action of Surfactant, galvanic deposit is at α-PbO
2carbon nano tube modified fluorine-containing β-PbO on middle layer 3
2surfactivity layer 4.
Preparation method is as follows: first with 120 order flint papers polishings titanium board substrates (30 millimeters * 50 millimeters * 0.8 millimeter), then with 600 orders and 1200 object fine sandpapers, polish to titanium board substrate and present silvery white metalluster successively, with deionized water rinsing; The titanium board substrate of polishing is placed in to acetone supersound process 10 minutes, wipe oil; Again the titanium board substrate after acetone supersound process is placed in to deionized water for ultrasonic and processes 10 minutes, remove acetone and other impurity; Then the titanium board substrate after deionized water for ultrasonic is processed is immersed in oxalic acid etching liquid (oxalic acid etching liquid is that 150 grams of oxalic acid are dissolved in 1 liter of deionized water formulated) 85 degrees Celsius of lower etchings 2 hours, takes out and be placed on oxalic acid and preserve in liquid (it is that 10g gram of oxalic acid is dissolved in 1 liter of deionized water formulated that oxalic acid is preserved liquid) and preserve.Tin trichloride and four antimony chlorides are dissolved in and in concentrated hydrochloric acid and isopropyl alcohol mixture, make coating liquid (20 grams of SnCl
4, 2.0 grams of SgCl
3, 13 milliliters of mass concentrations are 37% concentrated hydrochloric acid, 87 milliliters of Virahols), by being kept at oxalic acid, preserve the titanium board substrate taking-up in liquid, utilize washed with de-ionized water surface, coating liquid is coated on clean titanium board substrate, in electrically heated drying cabinet, under 120 degrees Celsius, dry 10 minutes, again the titanium board substrate after drying is placed in to 500 degrees Celsius of lower roastings of retort furnace 10 minutes, so repeat 8 times, last roasting time in retort furnace is 1 hour, naturally cool to room temperature, obtain the titanium board substrate with tin-antimony oxide bottom.Using the titanium board substrate with tin-antimony oxide bottom as anode, using the stainless steel plate of homalographic as negative electrode, galvanic deposit α-PbO in 100 milliliters of electrodeposit liquids that are dissolved with 0.1 mol/L PbO and 3.5 mol/L sodium hydroxide
2middle layer, the current density of galvanic deposit is 3mA/cm
2, depositing temperature is 40 degrees Celsius, depositing time is 1 hour.After cleaning with deionized water, obtain with α-PbO
2the titanium board substrate in middle layer.Will be with α-PbO
2the titanium board substrate in middle layer is as anode, the stainless steel plate of homalographic is as negative electrode, galvanic deposit β-PbO in 100 milliliters of mixing solutionss that are mixed with 5 grams per liter carbon nanotubes, 0.1 grams per liter Sodium dodecylbenzene sulfonate, 0.5 mol/L lead nitrate, 0.05 mol/L Sodium Fluoride and 1 mol/L nitric acid
2surfactivity layer, depositing current density is 15mA/cm
2, depositing temperature is 65 degrees Celsius, depositing time is 1 hour, obtains the carbon nano tube modified fluorine-containing β-PbO preparing under Sodium dodecylbenzene sulfonate effect
2surfactivity layer (in order to reduce costs, the carbon nanotube in this process can pass through to filter, rinse recycling), as accompanying drawing 3.
Adopt this electrode as anode, the stainless steel plate of homalographic is as negative electrode, and interpole gap is 1 centimetre, para-chlorophenol in catalytic oxidation water, the concentration of para-chlorophenol is 50 mg/litre, the sodium sulfate of 0.05 mol/L is done supporting electrolyte, the volume of solution is 200 milliliters, and current density is 30mA/cm
2, temperature is 30 degrees Celsius, the clearance that reacts para-chlorophenol after 120 minutes is 99.31%, is 1.26 times of common titanium base Lead dioxide anode modifiedby fluorine resin; Reacting after 180 minutes total organic Carbon removal in solution and can reach 88.43%, is 1.56 times of common ti-supported lead dioxide electric pole.Adopting this electrode is that anode carries out accelerated life test, and in the sulphuric acid soln of 1 mol/L, temperature is under 60 degrees Celsius, 1A/cm
2current density under the weightlessness of 20 hours rear electrodes of electrolysis be 5.4mg/cm
2, according to the weightlessness of electrode, being directly proportional to the work-ing life of electrode known, the more common titanium base Lead dioxide anode modifiedby fluorine resin in work-ing life of the carbon nano tube modified titanium base Lead dioxide anode modifiedby fluorine resin of preparing under Sodium dodecylbenzene sulfonate effect improves 1.87 times.
Embodiment 2:
The preparation method of electrode is with embodiment 1.
Difference is the carbon nano tube modified fluorine-containing β-PbO of galvanic deposit adopting
2the electroplate liquid of surfactivity layer is 100 milliliters of mixing solutionss that are mixed with 5 grams per liter carbon nanotubes, 0.1 grams per liter cetyl trimethylammonium bromide, 0.5 mol/L lead nitrate, 0.05 mol/L Sodium Fluoride and 1 mol/L nitric acid, obtain the carbon nano tube modified Lead dioxide anode modifiedby fluorine resin preparing under cetyl trimethylammonium bromide effect, as accompanying drawing 4.
Adopt this electrode as anode, the stainless steel plate of homalographic is as negative electrode, and interpole gap is 1 centimetre, para-chlorophenol in catalytic oxidation water, the concentration of para-chlorophenol is 50 mg/litre, the sodium sulfate of 0.05 mol/L is done supporting electrolyte, the volume of solution is 200 milliliters, and current density is 30mA/cm
2, temperature is 30 degrees Celsius, reacts para-chlorophenol clearance after 120 minutes and can reach 92.83%, is 1.18 times of common titanium base Lead dioxide anode modifiedby fluorine resin; Reacting after 180 minutes total organic Carbon removal in solution and can reach 76.90%, is 1.36 times of common titanium base Lead dioxide anode modifiedby fluorine resin.Adopting this electrode is that anode carries out accelerated life test, and in the sulphuric acid soln of 1 mol/L, temperature is under 60 degrees Celsius, 1A/cm
2current density under the weightlessness of 20 hours rear electrodes of electrolysis be 6.5mg/cm
2, according to the weightlessness of electrode, being directly proportional to the work-ing life of electrode known, the more common titanium base Lead dioxide anode modifiedby fluorine resin in work-ing life of the carbon nano tube modified titanium base Lead dioxide anode modifiedby fluorine resin of preparing under cetyl trimethylammonium bromide effect improves 1.55 times.
Claims (7)
1. a carbon nano tube modified titanium base Lead dioxide anode modifiedby fluorine resin, is characterized in that: this electrode comprises:
Titanium board substrate;
The tin-antimony oxide bottom of heat deposition on titanium board substrate;
α-the PbO of galvanic deposit on tin-antimony oxide bottom
2middle layer;
Under Action of Surfactant, galvanic deposit is at α-PbO
2carbon nano tube modified fluorine-containing β-PbO on middle layer
2surfactivity layer.
2. a preparation method for carbon nano tube modified titanium base Lead dioxide anode modifiedby fluorine resin, is characterized in that: the method comprises the following steps:
1., the pre-treatment of titanium matrix: first with 120 order flint papers polishing titanium board substrates, then polish to titanium board substrate and present silvery white metalluster with 600 orders and 1200 object fine sandpapers successively, with deionized water rinsing; The titanium board substrate of polishing is placed in to acetone supersound process 5 ~ 10 minutes, wipe oil; Again the titanium board substrate after acetone supersound process is placed in to deionized water for ultrasonic and processes 5 ~ 10 minutes, remove acetone and other impurity; Then the titanium board substrate after deionized water for ultrasonic is processed is immersed in oxalic acid etching liquid under 80 degrees Celsius ~ micro-condition of boiling to etching 1 ~ 4 hour, after taking-up, the titanium board substrate after etching is placed in to oxalic acid and preserves liquid and preserve;
2., the preparation of tin-antimony oxide bottom: tin trichloride and four antimony chlorides are dissolved in concentrated hydrochloric acid and isopropyl alcohol mixture and make coating liquid, on titanium board substrate surface after processing during 1. coating liquid is coated on, in electrically heated drying cabinet, under 120 degrees Celsius, dry 10 minutes, again the titanium board substrate of oven dry is placed in to 500 degrees Celsius of lower roastings of retort furnace 10 minutes, so repeat 5 to 10 times, last roasting time in retort furnace is 1 hour, naturally cools to room temperature;
3., α-PbO
2the preparation in middle layer: the titanium board substrate with tin-antimony oxide bottom that 2. step is prepared is as anode, the stainless steel plate of homalographic is as negative electrode, galvanic deposit α-PbO in being dissolved with the sodium hydroxide solution of PbO
2middle layer, the current density of galvanic deposit is 1 ~ 5mA/cm
2, depositing temperature is 30 ~ 60 degrees Celsius, depositing time is 0.5 ~ 2 hour;
4., carbon nano tube modified fluorine-containing β-PbO
2the preparation of surfactivity layer: step is made in 3. with α-PbO
2the titanium board substrate in middle layer is as anode, and the stainless steel plate of homalographic is as negative electrode, the carbon nano tube modified fluorine-containing β-PbO of galvanic deposit in the fluorine-containing lead nitrate solution of the acidity that is mixed with carbon nanotube and tensio-active agent
2surfactivity layer, the current density of galvanic deposit is 5 ~ 30mA/cm
2, depositing temperature is 45 ~ 85 degrees Celsius, depositing time is 0.5 ~ 2 hour.
3. the preparation method of a kind of carbon nano tube modified titanium base Lead dioxide anode modifiedby fluorine resin according to claim 2, is characterized in that: the oxalic acid etching liquid of step described in is 1. that 87 ~ 176 grams of oxalic acid are dissolved in 1 liter of deionized water formulated; It is that 10 grams of oxalic acid are dissolved in 1 liter of deionized water formulated that described oxalic acid is preserved liquid.
4. the preparation method of a kind of carbon nano tube modified titanium base Lead dioxide anode modifiedby fluorine resin according to claim 2, is characterized in that: the coating liquid of step described in is 2. to be that 10 ~ 15 milliliters of 37% concentrated hydrochloric acids, 50 ~ 100 milliliters of preparations of Virahol are made by 15 ~ 25 grams of tin tetrachloride, 1 ~ 5 gram of butter of antimony, mass concentration.
5. the preparation method of a kind of carbon nano tube modified titanium base Lead dioxide anode modifiedby fluorine resin according to claim 2, is characterized in that: step 3. described in galvanic deposit α-PbO
2the solution composition in middle layer is 0.05 ~ 0.12 mol/L PbO, 3.0 ~ 4.0 mol/L sodium hydroxide.
6. the preparation method of a kind of carbon nano tube modified titanium base Lead dioxide anode modifiedby fluorine resin according to claim 2, is characterized in that: the galvanic deposit carbon nano tube modified fluorine-containing β-PbO of step described in 4.
2the solution composition of surfactivity layer is lead nitrate 0.4 ~ 0.6 mol/L, nitric acid 0.09 ~ 1.1 mol/L, Sodium Fluoride 0.01 ~ 0.06 mol/L, tensio-active agent 0.05 ~ 5 grams per liter, carbon nanotube 0.5 ~ 20 grams per liter.
7. the preparation method of a kind of carbon nano tube modified titanium base Lead dioxide anode modifiedby fluorine resin according to claim 2, is characterized in that: described tensio-active agent is Sodium dodecylbenzene sulfonate, sodium laurylsulfonate or cetyl trimethylammonium bromide.
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