CN106809918B - A kind of carbon nano tube modified lead dioxide electrode and preparation method thereof - Google Patents

A kind of carbon nano tube modified lead dioxide electrode and preparation method thereof Download PDF

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CN106809918B
CN106809918B CN201510852363.2A CN201510852363A CN106809918B CN 106809918 B CN106809918 B CN 106809918B CN 201510852363 A CN201510852363 A CN 201510852363A CN 106809918 B CN106809918 B CN 106809918B
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CN106809918A (en
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段小月
常立民
刘伟
赵雪松
任新
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Jilin Normal University
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    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
    • C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D15/00—Electrolytic or electrophoretic production of coatings containing embedded materials, e.g. particles, whiskers, wires
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D9/00—Electrolytic coating other than with metals
    • C25D9/04—Electrolytic coating other than with metals with inorganic materials
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
    • C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
    • C02F1/46104—Devices therefor; Their operating or servicing
    • C02F1/46109—Electrodes
    • C02F2001/46133—Electrodes characterised by the material
    • C02F2001/46138—Electrodes comprising a substrate and a coating
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
    • C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
    • C02F1/46104—Devices therefor; Their operating or servicing
    • C02F1/46109—Electrodes
    • C02F2001/46152—Electrodes characterised by the shape or form
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/30—Organic compounds
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/30—Organic compounds
    • C02F2101/36—Organic compounds containing halogen

Abstract

The carbon nano tube modified lead dioxide electrode and preparation method thereof that the present invention provides a kind of for electrocatalytic oxidation process.The preparation method of the lead dioxide electrode includes titanium plate pretreatment, heat deposition tin-antimony oxide bottom, electro-deposition α-PbO2Middle layer, electro-deposition β-PbO2Internal layer, electrophoresis carbon nanotube interlayer, electro-deposition β-PbO2Surface layer.Carbon nano tube modified lead dioxide electrode prepared by the present invention has the advantages that strong large specific surface area, hydroxyl radical free radical generation ability, the active height of electrocatalytic oxidation and long service life, is a kind of electrode material suitable for electrocatalytic oxidation process for having development potentiality.

Description

A kind of carbon nano tube modified lead dioxide electrode and preparation method thereof
Technical field
The present invention relates to a kind of carbon nano tube modified lead dioxide electrodes and preparation method thereof, and are used for electro-catalysis Oxidation removal organic pollutants belong to water treatment technology and electrochemical field.
Background technique
In recent years, Electrocatalytic Oxidation because have do not consume or seldom consume chemical reagent, do not bring secondary pollution, operation The advantages of other methods such as easy, the energy mineralising refractory organic of control hardly match, it has also become water treatment technology is ground Study carefully hot spot.But the disadvantages of there is also the current efficiency of electrode is low, and electrode life is short or electrode involves great expense at present.Therefore how to make It is standby provided high electrocatalytic oxidation activity, high stability, and cheap electrode and be one of the area research important ask Topic.
Lead dioxide electrode is relatively broad one of the electrode material of research, it is conductive it is good, corrosion resistance is strong, cost Low, the features such as preparation method is simple, oxygen evolution potential is higher, oxidability is stronger.But lead dioxide electrode is in use process There are still current efficiency is low and the shorter disadvantage of service life.Therefore, in recent years, a large amount of scholar is dedicated to brown lead oxide electricity Pole is effectively modified, to improve the current efficiency and stability of lead dioxide electrode.Such as patent CN101054684A is mentioned For a kind of preparation method of Lead dioxide anode modifiedby fluorine resin, lead dioxide electrode obtained small, binding force with coating internal stress The advantage of length of good and electrode life；Patent CN101417831 proposes a kind of high absorption property particle (such as Powdered Activated Carbon or shell Glycan) and a kind of modified titanium-based Lead dioxide anode modifiedby fluorine resin of active metal (such as bismuth, nickel, lanthanum, cerium, erbium), it is made with electrode The advantage that valence is lower, oxidation organic pollutants activity is higher, internal stress is small and electrode life is long.
Carbon nanotube is as monodimension nanometer material, and light-weight, hexagonal structure connection is perfect, has many abnormal power , electricity and chemical property.Goed deep into its wide application prospect also not with carbon nanotube and nano materials research in recent years It shows disconnectedly.For this purpose, it is proposed that introducing carbon nanotubes in the active layer of lead dioxide electrode, to improve electrode The service life of electrocatalytic oxidation activity and electrode.
Summary of the invention
The object of the present invention is to provide a kind of carbon nano tube modified lead dioxide electrodes and preparation method thereof, and utilizing should Electrode Electro-catalytic Oxidation Process organic pollutants, carbon nano tube modified lead dioxide electrode obtained have specific surface area Greatly, the advantages that electrocatalytic oxidation activity height, long service life, simple, cheap preparation method.
The object of the present invention is achieved like this, which includes:
Titanium plate matrix；
Tin-antimony oxide bottom of the heat deposition on titanium plate matrix；
α-the PbO being electrodeposited on tin-antimony oxide bottom2Middle layer；
It is electrodeposited in α-PbO2β-PbO in middle layer2Internal layer；
Electrophoresis is in β-PbO2Carbon nanotube interlayer on internal layer；
β-the PbO being electrodeposited on carbon nanotube interlayer2Outer layer.
The preparation method of the carbon nano tube modified lead dioxide electrode the following steps are included:
1., the pretreatment of Titanium base: first with the sand paper of 120 mesh, 600 mesh and 1200 mesh successively polish titanium plate matrix until Silvery white metallic luster is presented；The titanium plate matrix polished is sequentially placed into acetone and deionized water again and is ultrasonically treated 10 points Clock removes the greasy dirt and other impurity on titanium plate surface；Then the titanium plate matrix after ultrasonic treatment is immersed in oxalic acid etching liquid 80 DEG C ~ it is slightly boiled under conditions of etch 2 hours, after taking-up by the titanium plate matrix after etching be placed in oxalic acid save liquid in save.
The oxalic acid etching liquid is that 150 grams of oxalic acid are dissolved in 1 liter of deionized water, stirs evenly and is formulated；It is described Oxalic acid save liquid be that 10 grams of oxalic acid are dissolved in 1 liter of deionized water, stir evenly and be formulated.
2., the preparation of tin-antimony oxide bottom: by tin tetrachloride and antimony trichloride be dissolved in concentrated hydrochloric acid and isopropanol mix it is molten Coating liquid is made in liquid, coating liquid is coated in 1. on treated titanium plate matrix surface, in electrically heated drying cabinet at 120 DEG C Drying 10 minutes, then the titanium plate matrix of drying is placed in Muffle furnace at 500 DEG C and is roasted 10 minutes, it is so repeated 10 times, finally Once the calcining time in Muffle furnace is 1 hour, cooled to room temperature.
③、α-PbO2The preparation of middle layer: the 2. titanium plate matrix with tin-antimony oxide bottom that step is prepared as Anode, the stainless steel plate of homalographic is as cathode, the electro-deposition α-PbO in the alkali plating solution dissolved with PbO2Middle layer, between electrode Away from being 3cm, the current density of electro-deposition is 3mA/cm2, depositing temperature is 40 DEG C, and sedimentation time is 1 hour, and electrodeposition process stirs It mixes, after electro-deposition, α-PbO will be had with deionized water2The titanium plate of middle layer is cleaned.
④、β-PbO2The preparation of internal layer: by step 3. in obtained have α-PbO2The titanium plate matrix of middle layer is as sun Pole, the stainless steel plate of homalographic is as cathode, the electro-deposition β-PbO in acid fluorine-containing plumbi nitras plating solution2Internal layer, electrode spacing are 3cm, the current density of electro-deposition are 15mA/cm2, depositing temperature is 65 DEG C, and sedimentation time is 30min, and electrodeposit liquid volume is 100mL stirs in deposition process, after electro-deposition, will have β-PbO with deionized water2The titanium plate of internal layer is cleaned.
5., the preparation of carbon nanotube interlayer: by step 4. in obtained have β-PbO2The titanium plate matrix of internal layer is as sun Pole, the stainless steel plate of homalographic is as cathode, and the electrophoresis carbon nanotube interlayer in carbon nano tube suspension, electrode spacing is 3cm, Electrophoretic voltage is 10-30V, and electrophoresis time is 5-20min, and suspension vol is 100mL, is operated at room temperature, in electrophoresis process not It stirs, dries the titanium plate with carbon nanotube interlayer 1 hour in 50 DEG C after electrophoresis.
⑥、β-PbO2The preparation of outer layer: using step 5. in the obtained titanium plate matrix with carbon nanotube interlayer as positive Pole, the stainless steel plate of homalographic is as cathode, electrode spacing 3cm, the electro-deposition β-PbO in acid fluorine-containing plumbi nitras plating solution2Outside Layer, the current density of electro-deposition is 15mA/cm2, depositing temperature is 65 DEG C, and sedimentation time is 5-15min, and electrodeposit liquid volume is 100mL, deposition process do not stir, and will have β-PbO with deionized water after deposition2The lead dioxide electrode of outer layer is cleaned.
Step 2. described in coating liquid be by 20 grams of tin tetrachloride, 2 grams of antimony trichloride, mass concentration be 37% concentrated hydrochloric acid 13 milliliters, 87 milliliters of isopropanol mixing, and stir evenly and be formulated.
Step 3. described in the alkali plating solution dissolved with PbO be to be add to deionized water PbO and sodium hydroxide, heating Stirring is completely dissolved to PbO, and cooled to room temperature configures, and each component content of plating solution is 0.1 mol/L of PbO, hydrogen 3.5 mol/L of sodium oxide molybdena.
Step 4. with step 6. described in the fluorine-containing plumbi nitras plating solution of acidity be to be dissolved in plumbi nitras, nitric acid, sodium fluoride In deionized water, stir evenly and be formulated, each component content of plating solution be 0.5 mol/L of plumbi nitras, 1.0 moles of nitric acid/ It rises, 0.05 mol/L of sodium fluoride.
Step 5. the carbon nano tube suspension be by neopelex (or the yin such as dodecyl sodium sulfate from Sub- surfactant) it is dissolved in deionized water and obtains A liquid, then carbon nanotube is added in A liquid, is stirred evenly and ultrasound 30-60min is made, and each component content is 0.5 ~ 2 grams per liter of carbon nanotube, neopelex (or dodecane in suspension The anionic surfactants such as base sodium sulfonate) 0.01 ~ 0.1 grams per liter.
The present invention has a characteristic that
(1) the surface-active layer of the carbon nano tube modified lead dioxide electrode prepared by the present invention is by β-PbO2Internal layer, Carbon nanotube interlayer and β-PbO2Outer layer composition.
(2) the carbon nano tube modified lead dioxide electrode Electro-catalytic Oxidation Process parachlorophenol prepared by the present invention, solution Middle total organic Carbon removal is 2.1 times of common lead dioxide electrode, service life up to common lead dioxide electrode 1.7 Times.
(3) difficult for biological degradation organic contamination in the carbon nano tube modified lead dioxide electrode degradation water prepared by the present invention Object, simple process, effect is obvious, convenient for management, and the processing method for being suitable for organic wastewater, which is independently operated, also can be used as biology The pretreatment technology of method and other technical tie-ups use.
Detailed description of the invention
Fig. 1 is the structural schematic diagram of carbon nano tube modified lead dioxide electrode of the present invention.
Fig. 2 is the scanning electron microscope (SEM) photograph of common lead dioxide electrode.
Fig. 3 is electro-deposition β-PbO of the present invention2Internal layer 30min- electrophoresis carbon nanotube interlayer 10min- electro-deposition β- PbO2The scanning electron microscope (SEM) photograph of the carbon nano tube modified lead dioxide electrode of outer layer 5min.
Fig. 4 is electro-deposition β-PbO of the present invention2Internal layer 30min- electrophoresis carbon nanotube interlayer 10min- electro-deposition β- PbO2The scanning electron microscope (SEM) photograph of the carbon nano tube modified lead dioxide electrode of outer layer 10min.
Specific embodiment
For the ease of the comparison of product of the present invention, we are prepared for common titanium-based Lead dioxide anode modifiedby fluorine resin, specific to prepare Method is as follows:
(1) successively with 120 mesh, 600 mesh and 1200 mesh sand paper polishing titanium plate matrix (30 millimeters × 50 millimeters × 0.8 milli Rice), until silvery white metallic luster is presented in titanium plate matrix, the titanium plate matrix polished is sequentially placed into acetone and deionized water Ultrasonic treatment 10 minutes, removes the greasy dirt and other impurity of matrix surface；Then the titanium plate matrix after ultrasonic treatment is immersed in (oxalic acid etching liquid is that 150 grams of oxalic acid are dissolved in 1 liter of deionized water, stirs evenly and is formulated) is at 85 DEG C in oxalic acid etching liquid Lower etching 2 hours, taking-up is placed on oxalic acid preservation liquid, and (it is that 10 grams of oxalic acid are dissolved in 1 liter of deionized water that oxalic acid, which saves liquid, stirring Uniformly be formulated) in save.
(2) tin tetrachloride and antimony trichloride are dissolved in concentrated hydrochloric acid and isopropyl alcohol mixture and coating liquid (coating liquid is made Being is that 37% concentrated hydrochloric acid, 87 milliliters of isopropanols are mixed, and stirred by 20 grams of tin tetrachlorides, 2 grams of antimony trichlorides, 13 milliliters of mass concentrations Mix and be uniformly formulated), the titanium plate matrix that will be stored in step (1) in oxalic acid preservation liquid takes out, and is cleaned using deionized water Coating liquid is coated on clean titanium plate matrix, dries 10 minutes at 120 DEG C in electrically heated drying cabinet by surface, then will drying Titanium plate matrix afterwards is placed in Muffle furnace at 500 DEG C and roasts 10 minutes, is so repeated 10 times, for the last time the roasting in Muffle furnace Burning the time is 1 hour, and cooled to room temperature obtains the titanium plate matrix with tin-antimony oxide bottom.
(3) using the titanium plate matrix with tin-antimony oxide bottom of step (2) preparation as anode, with the stainless of homalographic Steel plate is as cathode, at 100 milliliters dissolved with electro-deposition in the alkali plating solution of 0.1 mol/L PbO and 3.5 mol/L sodium hydroxides α-PbO2Middle layer, electrode spacing are 3cm, and the current density of electro-deposition is 3mA/cm2, depositing temperature is 40 DEG C, and sedimentation time is It 1 hour, is stirred in electrodeposition process.It is washed with deionized water, is obtained with α-PbO after electro-deposition2The titanium plate of middle layer Matrix.
(4) step (3) preparation is had into α-PbO2The titanium plate matrix of middle layer is as anode, the stainless steel plate of homalographic As cathode, in 100 milliliters of acidity containing 0.5 mol/L plumbi nitras, 0.05 mol/L sodium fluoride and 1 mol/L nitric acid Electro-deposition β-PbO in plating solution2Surface-active layer, electrode spacing are 3cm, and electro-deposition current density is 15mA/cm2, depositing temperature is 65 DEG C, sedimentation time is 1 hour, electrodeposition process stirring.It is washed with deionized water after electro-deposition, what is prepared is general Logical lead dioxide electrode, as shown in Fig. 2: as can be seen from Fig., common lead dioxide electrode is by a large amount of pyramid titanium dioxides Leading crystal particle packing forms.
Use the common lead dioxide electrode being prepared for anode, the stainless steel plate of homalographic is cathode, electrocatalytic oxidation Change parachlorophenol in water, the concentration of parachlorophenol is 50 mg/litres, and the sodium sulphate of 0.05 mol/L does supporting electrolyte, solution Volume be 200 milliliters, electrode spacing be 1 centimetre, electrocatalytic oxidation current density be 20mA/cm2, temperature is 30 DEG C, reaction The removal rate of parachlorophenol is 62.5% after 120 minutes, and total organic Carbon removal reaches 30.8% in solution after reaction 180 minutes.
Using the common lead dioxide electrode being prepared as working electrode, platinum electrode is to electrode, in the sulphur of 1 mol/L In acid solution, 1A/cm2Current density under measure electrode reinforcing life be 56 hours.
The specific embodiment for preparing product of the present invention is as follows:
Embodiment 1:
As shown in Fig. 1: the structure of carbon nano tube modified lead dioxide electrode of the invention includes:
Titanium plate matrix 1；
Tin-antimony oxide bottom 2 of the heat deposition on titanium plate matrix；
α-the PbO being electrodeposited on tin-antimony oxide bottom 22Middle layer 3；
It is electrodeposited in α-PbO2β-PbO in middle layer 32Internal layer 4.
Electrophoresis is in β-PbO2Carbon nanotube interlayer 5 on internal layer 4.
β-the PbO being electrodeposited on electrical carbon nanotube interlayer 52Outer layer 6.
The preparation method is as follows:
(1) successively with 120 mesh, 600 mesh and 1200 mesh sand paper polishing titanium plate matrix (30 millimeters × 50 millimeters × 0.8 milli Rice), until silvery white metallic luster is presented in titanium plate matrix, the titanium plate matrix polished is sequentially placed into acetone and deionized water Ultrasonic treatment 10 minutes, removes the greasy dirt and other impurity of matrix surface；Then the titanium plate matrix after ultrasonic treatment is immersed in (oxalic acid etching liquid is that 150 grams of oxalic acid are dissolved in 1 liter of deionized water, stirs evenly and is formulated) is at 85 DEG C in oxalic acid etching liquid Lower etching 2 hours, taking-up is placed on oxalic acid preservation liquid, and (it is that 10 grams of oxalic acid are dissolved in 1 liter of deionized water that oxalic acid, which saves liquid, stirring Uniformly be formulated) in save.
(2) tin tetrachloride and antimony trichloride are dissolved in concentrated hydrochloric acid and isopropyl alcohol mixture and coating liquid (coating liquid is made Being is that 37% concentrated hydrochloric acid, 87 milliliters of isopropanols are mixed, and stirred by 20 grams of tin tetrachlorides, 2 grams of antimony trichlorides, 13 milliliters of mass concentrations Mix and be uniformly formulated), the titanium plate matrix that will be stored in step (1) in oxalic acid preservation liquid takes out, and is cleaned using deionized water Coating liquid is coated on clean titanium plate matrix, dries 10 minutes at 120 DEG C in electrically heated drying cabinet by surface, then will drying Titanium plate matrix afterwards is placed in Muffle furnace at 500 DEG C and roasts 10 minutes, is so repeated 10 times, for the last time the roasting in Muffle furnace Burning the time is 1 hour, and cooled to room temperature obtains the titanium plate matrix with tin-antimony oxide bottom.
(3) using the titanium plate matrix with tin-antimony oxide bottom of step (2) preparation as anode, with the stainless of homalographic Steel plate is as cathode, at 100 milliliters dissolved with electro-deposition in the alkali plating solution of 0.1 mol/L PbO and 3.5 mol/L sodium hydroxides α-PbO2Middle layer, electrode spacing are 3cm, and electro-deposition current density is 3mA/cm2, depositing temperature is 40 DEG C, and sedimentation time is 1 Hour, it is stirred in electrodeposition process.It is washed with deionized water, is obtained with α-PbO after electro-deposition2The titanium plate base of middle layer Body.
(4) step (3) preparation is had into α-PbO2The titanium plate matrix of middle layer is as anode, the stainless steel plate of homalographic As cathode, in 100 milliliters of acidity containing 0.5 mol/L plumbi nitras, 0.05 mol/L sodium fluoride and 1 mol/L nitric acid Electro-deposition β-PbO in plating solution2Internal layer, electrode spacing are 3cm, and electro-deposition current density is 15mA/cm2, depositing temperature is 65 DEG C, Sedimentation time is 30min, is stirred in electrodeposition process.It is washed with deionized water, is obtained with β-PbO after electro-deposition2It is interior The titanium plate matrix of layer.
(5) step (4) preparation is had into β-PbO2The titanium plate matrix of internal layer is made as anode, the stainless steel plate of homalographic For cathode, in carbon nano tube suspension, (suspension is to be dissolved in 0.05 gram of neopelex in 1 liter of deionized water to obtain Be added in A liquid to A liquid, then by 1 gram of carbon nanotube, stir evenly and ultrasound 30min it is made) in electrophoresis carbon nanotube interlayer, Electrode spacing is 3cm, and electrophoretic voltage is 30V, and electrophoresis time is 10 minutes, and suspension vol is 100mL, is operated at room temperature, no It stirs, is dried 1 hour after electrophoresis in 50 DEG C, obtain the titanium plate matrix with carbon nanotube interlayer and (in order to reduce cost, be somebody's turn to do Carbon nanotube in the process can be by filtering, rinsing recycling and reusing).
(6) using the titanium plate matrix with carbon nanotube interlayer of step (5) preparation as anode, the stainless steel plate of homalographic As cathode, there is the acid plating of 0.5 mol/L plumbi nitras, 0.05 mol/L sodium fluoride and 1 mol/L nitric acid at 100 milliliters Electro-deposition β-PbO in liquid2Outer layer, electrode spacing are 3cm, and electro-deposition current density is 15mA/cm2, depositing temperature is 65 DEG C, is sunk The product time is 5min, is not stirred in electrodeposition process.It is washed with deionized water after electro-deposition, obtains carbon nano tube modified two Lead dioxide electrode, as shown in Fig. 3: from the figure 3, it may be seen that foring a large amount of β-PbO in carbon nanotube sandwiching surface2Crystal grain, The crystallite dimension of these crystal is significantly less than common lead dioxide electrode, and not only effectively carbon nanotube was fixed on matrix, but also There are a large amount of carbon nanotubes to be exposed to electrode surface.Obvious small β-PbO2It is bigger that crystal grain and exposed carbon nanotube have electrode Specific surface area.
Use the carbon nano tube modified lead dioxide electrode being prepared for anode, the stainless steel plate of homalographic is cathode, Parachlorophenol in electrocatalytic oxidation water, the concentration of parachlorophenol are 50 mg/litres, and the sodium sulphate of 0.05 mol/L does support electricity Xie Zhi, the volume of solution are 200 milliliters, and electrode spacing is 1 centimetre, and electrocatalytic oxidation current density is 20mA/cm2, temperature is 30 DEG C, the removal rate of parachlorophenol is 74.2% after reaction 120 minutes, and total organic Carbon removal reaches in solution after reaction 180 minutes To 50.8%.
Using the carbon nano tube modified lead dioxide electrode being prepared as working electrode, platinum electrode is to rub to electrode in 1 You/liter sulfuric acid solution in, 1A/cm2Current density under measure electrode reinforcing life be 72 hours, be common titanium-based it is fluorine-containing 1.3 times of lead dioxide electrode.
Embodiment 2:
The preparation method is the same as that of Example 1 for electrode.
Except that electro-deposition β-PbO2The time of outer layer is 10min, obtains carbon nano tube modified lead dioxide electrode, Electrode pattern is as shown in Figure 4: as shown in Figure 4, foring incomplete β-PbO in carbon nanotube sandwiching surface2Crystalline film has A small amount of carbon nanotube is exposed to electrode surface, the β-PbO around carbon nanotube2Crystal grain sizes are significantly less than common dioxy Change lead electrode.
Use the carbon nano tube modified lead dioxide electrode being prepared for anode, the stainless steel plate of homalographic is cathode, Electrode spacing is 1 centimetre, parachlorophenol in electrocatalytic oxidation water, and the concentration of parachlorophenol is 50 mg/litres, 0.05 mol/L Sodium sulphate do supporting electrolyte, the volume of solution is 200 milliliters, and electrode spacing is 1 centimetre, and electrocatalytic oxidation current density is 20mA/cm2, temperature is 30 DEG C, and the removal rate of parachlorophenol is 87.4% after reaction 120 minutes, after reaction 180 minutes in solution Total organic Carbon removal reaches 64.7%.
Using the carbon nano tube modified lead dioxide electrode being prepared as working electrode, platinum electrode is to rub to electrode in 1 You/liter sulfuric acid solution in, 1A/cm2Current density under measure electrode reinforcing life be 95 hours, be common titanium-based it is fluorine-containing 1.7 times of lead dioxide electrode.

Claims (1)

1. a kind of carbon nano tube modified lead dioxide electrode, which includes the tin of titanium plate matrix, heat deposition on titanium plate matrix Sb oxide bottom, the α-PbO being electrodeposited on tin-antimony oxide bottom2Middle layer, it is characterised in that: it further includes electro-deposition In α-PbO2β-PbO in middle layer2Internal layer, electrophoresis is in β-PbO2Carbon nanotube interlayer and carbon nanotube is electrodeposited on internal layer β-PbO on interlayer2Outer layer；
Above-mentioned carbon nano tube modified lead dioxide electrode is prepared by the following method, and the method includes the pretreatments of Titanium base, tin The preparation of sb oxide bottom, α-PbO2The preparation of middle layer, it is characterised in that further include β-PbO2The preparation of internal layer, carbon nanometer The preparation of pipe clamp layer and β-PbO2Three steps of preparation of outer layer；
β-the PbO2The preparation of internal layer is will to have α-PbO2The titanium plate matrix of middle layer is as anode, the stainless steel of homalographic Plate is as cathode, the electro-deposition β-PbO in acid fluorine-containing plumbi nitras plating solution2Internal layer, electrode spacing are 3cm, the electric current of electro-deposition Density is 15mA/cm2, depositing temperature is 65 DEG C, and sedimentation time is 30min, and plating solution volume is 100mL, is stirred in electrodeposition process It mixes, β-PbO will be had after electro-deposition2The titanium plate of internal layer is washed with deionized water；The preparation of the carbon nanotube interlayer It is that will have β-PbO2The titanium plate matrix of internal layer suspends as cathode in carbon nanotube as anode, the stainless steel plate of homalographic Electrophoresis carbon nanotube interlayer in liquid, electrode spacing are 3cm, and electrophoretic voltage is 10-30V, and electrophoresis time is 5-20min, suspension Volume is 100mL, is operated at room temperature, is not stirred in electrophoresis process, after electrophoresis by with carbon nanotube interlayer titanium plate in 50 DEG C dry 1 hour；β-the PbO2The preparation of outer layer be will the titanium plate matrix with carbon nanotube interlayer as anode, etc. The stainless steel plate of area is as cathode, the electro-deposition β-PbO in acid fluorine-containing plumbi nitras plating solution2Outer layer, electrode spacing are 3cm, The current density of electro-deposition is 15mA/cm2, depositing temperature is 65 DEG C, and sedimentation time is 3-15min, and plating solution volume is 100mL, It is not stirred in electrodeposition process, β-PbO will be had after electro-deposition2The lead dioxide electrode of outer layer is washed with deionized water； The carbon nano tube suspension is added to carbon nanotube in neopelex or sodium dodecyl sulfate solution, It stirs evenly and ultrasound 30-60min is made, each component content is 0.5 ~ 2 grams per liter of carbon nanotube, dodecyl in suspension liquid 0.01 ~ 0.1 grams per liter of benzene sulfonic acid sodium salt or dodecyl sodium sulfate.
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