CN108914122A - A kind of preparation method of ti-lead dioxide anode - Google Patents

A kind of preparation method of ti-lead dioxide anode Download PDF

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CN108914122A
CN108914122A CN201810853584.5A CN201810853584A CN108914122A CN 108914122 A CN108914122 A CN 108914122A CN 201810853584 A CN201810853584 A CN 201810853584A CN 108914122 A CN108914122 A CN 108914122A
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anode
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CN108914122B (en
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代春龙
邹宗海
魏明勇
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Shandong Longantai Environmental Protection Sci-Tech Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • C23C28/04—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings of inorganic non-metallic material
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
    • C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
    • C02F1/46104—Devices therefor; Their operating or servicing
    • C02F1/46109—Electrodes
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
    • C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
    • C23C18/1204—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material inorganic material, e.g. non-oxide and non-metallic such as sulfides, nitrides based compounds
    • C23C18/1208—Oxides, e.g. ceramics
    • C23C18/1216—Metal oxides
    • 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
    • C25D9/06—Electrolytic coating other than with metals with inorganic materials by anodic processes
    • 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
    • C02F2001/46142—Catalytic coating
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2209/00—Controlling or monitoring parameters in water treatment
    • C02F2209/08—Chemical Oxygen Demand [COD]; Biological Oxygen Demand [BOD]

Abstract

A kind of preparation method of ti-lead dioxide anode, includes the following steps：Titanium-based matrix is pre-processed；Tin tetrachloride and antimony trichloride are dissolved in the isopropanol containing hydrochloric acid, and are coated on titanium plate matrix surface, after drying and roasting, obtains the electrode with tin-antimony oxide bottom；Using the electrode with tin-antimony oxide bottom as anode, titanium plate is cathode, the electro-deposition α-PbO in the sodium hydroxide plating solution dissolved with PbO2Middle layer；Be anode by titanium plate, titanium plate is cathode, electro-deposition be made containing ceria, bait, fluorine modification β-PbO2Active layer obtains the ti-lead dioxide anode.Polar board surface even compact, long service life prepared by this preparation method；Electrochemistry oxidation performance is high；Processing cost is low.

Description

A kind of preparation method of ti-lead dioxide anode
Technical field
The present invention relates to industrial wastewater electrocatalytic oxidation processing technology fields, more particularly, to a kind of electrocatalytic oxidation process In ceria and bait codope ti-lead dioxide anode preparation method.
Background technique
With the rapid development of modern industry, the growth that global economy is advanced by leaps and bounds, this is giving people's life band It is also produced while to facilitate largely containing toxic, harmful, Recalcitrant chemicals industrial wastewaters, if industrial wastewater is without place Reason is directly entered water body, serious pollution and destruction will be caused to environment, and then endanger human health.Therefore, industrial wastewater Processing it is urgent and can not be ignored.
The traditional processing method of industrial wastewater includes biochemical method, physical method, chemical method etc., these methods have reaction condition The disadvantages of harshness, secondary pollution, it is difficult to be really achieved the purpose of degradation of contaminant.Electrocatalytic Oxidation is based on conventional oxidation method On a kind of suitable processing Recalcitrant chemicals advanced oxidation processes, have efficiently, treatment conditions are mild, environment compatibility is good etc. Advantage.
Brown lead oxide has many advantages, such as that oxygen evolution potential is high, stability is good, good conductivity, corrosion-resistant, cheap, very early Someone is applied in industrial production as anode.With the research that deepens continuously to lead dioxide electrode, to solve without base Problems, the ti-supported lead dioxide electric poles such as the big, machining of the distortion of electrode existing for body lead dioxide electrode have obtained extensively Using.
Ti-supported lead dioxide electric pole good, easy to process, the titanium thermal expansion coefficient of conductive energy and brown lead oxide are close The advantages that, but still have the shortcomings that current efficiency is low and coating easily " passivation " service life is short in use.Therefore, lead to The method for crossing incorporation a small amount of additive in the plating solution improves electrode performance and is widely studied.
102280626 A of related patents CN discloses a kind of composite lead dioxide electrode plate and its manufacturing method, though this method So using titanium as substrate, successively there are transition zone, α-PbO2Middle layer, β-PbO2Active layer, but only in playing blunt transition zone The elements such as Pt, Ta, Ir are added to, and do not have improvement, therefore the pole plate β-prepared to the active layer that pole plate performance plays a crucial role PbO2Active layer is less desirable in terms of electrode density, electric conductivity, catalytic performance.
103014800 A of related patents CN discloses a kind of preparation of the graphite base lead dioxide catalysis electrode of cerium dopping Method, the method is using graphite as matrix, though α-PbO is successively coated in graphite primary surface2β-the PbO of middle layer and doping cerium2Activity Layer, but the method is with Ce3+As dopant, compared to CeO2, Ce3+Adulterate the β-PbO of preparation2Active layer surface is relatively rough, Crystal grain hole is larger, so its existing defects in corrosion resistance and service life.
Summary of the invention
The purpose of the present invention is to provide a kind of preparations for mixing ceria and the co-modified ti-lead dioxide anode of erbium Method, it is excellent that the brown lead oxide pole plate being prepared by this method has that oxidation activity is high, electric conductivity is strong, electrode life is long etc. Point can effectively remove the persistent organic pollutants in industrial wastewater.The technical method of use is：A kind of ti-supported lead dioxide electric sun The preparation method of pole, it is characterised in that：Include the following steps：
1) titanium-based matrix is pre-processed, to remove matrix surface impurity and obtain the good surface of process performance；
2) tin tetrachloride and antimony trichloride are dissolved in the isopropanol containing hydrochloric acid, and are coated on titanium plate matrix surface, 5-20min is roasted again after drying 10-15min at 120 DEG C, 8-10 times repeatedly, finally roasts 1.0-2.0h, is obtained with tin antimony The electrode of oxide underlayer；
3) using the electrode with tin-antimony oxide bottom as anode, titanium plate is cathode, in the sodium hydroxide for being dissolved with PbO Electro-deposition α-PbO in plating solution2Middle layer；
It 4) is anode by the titanium plate of step (3) preparation, titanium plate is cathode, is contained in the acidity of doping cerium dioxide and nitric acid bait In fluorine lead solution, the group of the fluorine-containing lead plating solution of the acidity containing ceria and nitric acid bait becomes Pb (NO3)2、HNO3、NaF、CeO2 And Er (NO3)3, electro-deposition be made containing ceria, bait, fluorine modification β-PbO2Active layer obtains the ti-supported lead dioxide electric sun Pole.
It include polishing and decontamination to the pretreatment that titanium-based matrix carries out in this method step 1) to obtain grey pitted skin surface It is handled with acid etch is included.
Suitable maturing temperature is 500 DEG C in step 2) of the present invention.
Tin tetrachloride and antimony trichloride are dissolved in the isopropanol containing hydrochloric acid in solution obtained in the step 2), The group of tin tetrachloride and antimony trichloride coating liquid becomes the SnCl of 500mmol/L4·5H2O, the SbCl of 60mmol/L3, isopropanol Volume ratio with concentrated hydrochloric acid is 20:1-20:10.
PbO sodium hydroxide plating solution group becomes 0.10mol/LPbO and 140g/L sodium hydroxide in step 3).
Electro-deposition α-PbO in step 3)2The sedimentation time of middle layer is 0.5-1.0h, and depositing temperature is 35-45 DEG C, and electricity is heavy Long-pending current density is 20mA/cm2, stirred with about 300-500 revs/min speed in electrodeposition process, pole plate spacing 1.5- 5cm。
The group of acid fluorine-containing lead plating solution becomes the Pb (NO of 0.5mol/L in step 4)3)2, 0.15mol/L HNO3、 The CeO of NaF, 1.8g/L of 0.012mol/L2And the Er (NO3) of 0.05g/L3。
Electro-deposition described in step 4) be made containing ceria, bait, fluorine modification β-PbO2The electrodeposition time of active layer For 1.0-2.0h, depositing temperature is 35-5045 DEG C, and electro-deposition current density is 35-45mA/cm2, with about in electrodeposition process 300-500 revs/min of speed stirring, pole plate spacing 1.5-5cm.
The beneficial effects of the present invention are：
1) polar board surface even compact, long service life prepared by.Doping cerium dioxide and erbium can hinder brown lead oxide brilliant The continuous growth of body refines crystal grain, to improve the service life of electrode.
2) electrochemistry oxidation performance is high.The doping of ceria and erbium can be such that electrode active surface site increases, to make Its electrochemical oxidation degradation capability increases.
3) processing cost is low, application easy to spread.Strong, COD of anode of lead dioxide electric conductivity of this method preparation etc. is gone Except high-efficient, reaction condition is mild, this greatly reduces the operating costs such as the electricity charge, medicament.
Specific embodiment
Description of specific embodiments of the present invention below.
The invention discloses a kind of preparation method of ti-lead dioxide anode, which includes the following steps：
1) titanium-based matrix is pre-processed, it, should to remove matrix surface impurity and obtain the good surface of process performance Surface preparation pretreatment includes that polishing, decontamination and acid etch processing, acid etching can get pitted skin.
2) tin tetrachloride and antimony trichloride are dissolved in the isopropanol containing hydrochloric acid, and are coated on titanium plate matrix surface, 5-20min is roasted again after drying 10-15min at 120 DEG C, 8-10 times repeatedly, finally roasts 1.0-2.0h, is obtained with tin antimony The electrode of oxide underlayer, tin tetrachloride and antimony trichloride are dissolved in the isopropanol containing hydrochloric acid in solution obtained, and four The group of stannic chloride and antimony trichloride coating liquid becomes the SnCl of 500mmol/L4·5H2O, the SbCl of 60mmol/L3, isopropanol with The volume ratio of concentrated hydrochloric acid is 20:1-20:10.Maturing temperature is preferably 500 DEG C in step 2).
3) using the electrode with tin-antimony oxide bottom as anode, titanium plate is cathode, in the sodium hydroxide for being dissolved with PbO Electro-deposition α-PbO in plating solution2Middle layer, PbO sodium hydroxide plating solution group become 0.10mol/LPbO and 140g/L sodium hydroxide.Electricity Deposit α-PbO2The sedimentation time of middle layer is 0.5-1.0h, and depositing temperature is 35-45 DEG C, and the current density of electro-deposition is 20mA/cm2, stirred with about 300-500 revs/min speed in electrodeposition process, pole plate spacing 1.5-5cm.
It 4) is anode by the titanium plate of step (3) preparation, titanium plate is cathode, is contained in the acidity of doping cerium dioxide and nitric acid bait In fluorine lead solution, the group of the fluorine-containing lead plating solution of the acidity containing ceria and nitric acid bait becomes Pb (NO3)2、HNO3、NaF、CeO2 And Er (NO3)3, electro-deposition be made containing ceria, bait, fluorine modification β-PbO2Active layer obtains the ti-supported lead dioxide electric sun Pole.The group of acid fluorine-containing lead plating solution becomes the Pb (NO of 0.5mol/L3)2, 0.15mol/L HNO3, 0.012mol/L NaF, The CeO of 1.8g/L2And Er (the NO of 0.05g/L3)3.Electro-deposition be made containing ceria, bait, fluorine modification β-PbO2Active layer Electrodeposition time is 1.0-2.0h, and depositing temperature is 35-50 DEG C, and electro-deposition current density is 35-45mA/cm2, electrodeposition process In stirred with about 300-500 revs/min speed, pole plate spacing 1.5-5cm.
Embodiment 1：
A kind of to mix ceria and the co-modified ti-lead dioxide anode of bait, preparation method is as follows：By 10*10cm*3mm Clear water rinses after titanium mesh plate is polished with sand paper, then 80 DEG C of heating oil removing 2h in 40% sodium hydroxide solution again, after clear water is clean Ebuillition of heated 2-3h in 10% oxalic acid solution again, until grey pitted skin occurs in web plate surface, clear water is rinsed well.
Tin tetrachloride and antimony trichloride are dissolved in the isopropanol containing hydrochloric acid, and are coated on titanium plate matrix surface, 5min is roasted at 500 DEG C again after drying 10min at 120 DEG C, 10 times repeatedly, finally 1.0h is roasted at 500 DEG C, is had The group of the electrode of tin-antimony oxide bottom, tin tetrachloride and antimony trichloride coating liquid becomes the SnCl of 500mmol/L4·5H2O、 The SbCl of 60mmol/L3, isopropanol 100mL, concentrated hydrochloric acid 15mL.
Using the electrode with tin-antimony oxide bottom as anode, titanium plate is cathode, is plated in the sodium hydroxide dissolved with PbO Electro-deposition α-PbO in liquid2Middle layer, PbO sodium hydroxide plating solution group become 0.10mol/LPbO and 140g/L sodium hydroxide, deposition Time is 1.0h, and depositing temperature is 45 DEG C, and the current density of electro-deposition is 20mA/cm2, with about 400 revs/min in electrodeposition process The stirring of clock rate degree, pole plate spacing 4cm.
Titanium plate by above step preparation is anode, and titanium plate is cathode, is contained in the acidity of doping cerium dioxide and nitric acid bait In fluorine lead solution, the group of the fluorine-containing lead plating solution of the acidity containing ceria and nitric acid bait becomes the Pb (NO of 0.5mol/L3)2、 The HNO of 0.15mol/L3, 0.012mol/L NaF, 1.8g/L CeO2And Er (the NO of 0.05g/L3)3, electro-deposition, which is made, contains two Cerium oxide, bait, fluorine modification β-PbO2Active layer, electrodeposition time 2.0h, depositing temperature are 45 DEG C, electro-deposition current density For 35-45mA/cm2, stirred with about 400 revs/min of speed in electrodeposition process, pole plate spacing 4cm.It obtains mixing ceria The co-modified ti-lead dioxide anode with bait.
Using this electrode plate as anode, stainless steel plate as cathode, certain factory's reverse osmosis concentrated water, annode area and yin are handled Pole-face product is 100cm2, for interpolar away from 3cm, input current intensity is 2.0A.The initial COD concentration of reverse osmosis concentrated water is 2000mg/ L, volume 1.0L, initial pH6.8, reaction carry out 2h, and COD removal rate reaches 77%.
Embodiment 2：
A kind of to mix ceria and the co-modified ti-lead dioxide anode of bait, preparation method is as follows：By 50*20cm*3mm Clear water rinses after titanium mesh plate is polished with sand paper, then 80 DEG C of heating oil removing 2h in 40% sodium hydroxide solution again, after clear water is clean Ebuillition of heated 2-3h in 10% oxalic acid solution again, until grey pitted skin occurs in web plate surface, clear water is rinsed well.
Tin tetrachloride and antimony trichloride are dissolved in the isopropanol containing hydrochloric acid, and are coated on titanium plate matrix surface, 15min is roasted at 500 DEG C again after drying 15min at 120 DEG C, 10 times repeatedly, finally 1.2h is roasted at 500 DEG C, obtains band There is an electrode of tin-antimony oxide bottom, the group of tin tetrachloride and antimony trichloride coating liquid becomes the SnCl of 500mmol/L4·5H2O、 The SbCl of 60mmol/L3, isopropanol 100mL, concentrated hydrochloric acid 50mL.
Using the electrode with tin-antimony oxide bottom as anode, titanium plate is cathode, is plated in the sodium hydroxide dissolved with PbO Electro-deposition α-PbO in liquid2Middle layer, PbO sodium hydroxide plating solution group become 0.10mol/LPbO and 140g/L sodium hydroxide, deposition Time is 1.0h, and depositing temperature is 35 DEG C, and the current density of electro-deposition is 20mA/cm2, with about 400 revs/min in electrodeposition process The stirring of clock rate degree, pole plate spacing 1.5cm.
Titanium plate by above step preparation is anode, and titanium plate is cathode, is contained in the acidity of doping cerium dioxide and nitric acid bait In fluorine lead solution, the group of the fluorine-containing lead plating solution of the acidity containing ceria and nitric acid bait becomes the Pb (NO of 0.5mol/L3)2、 The HNO of 0.15mol/L3, 0.012mol/L NaF, 1.8g/L CeO2And Er (the NO of 0.05g/L3)3, electro-deposition, which is made, contains two Cerium oxide, bait, fluorine modification β-PbO2Active layer, electrodeposition time 2.0h, depositing temperature are 45 DEG C, electro-deposition current density For 35-45mA/cm2, stirred with about 400 revs/min of speed in electrodeposition process, pole plate spacing 4cm is to get to mixing ceria The co-modified ti-lead dioxide anode with bait.
Using this electrode plate as anode, stainless steel plate as cathode, certain factory's reverse osmosis concentrated water, annode area and yin are handled Pole-face product is 100cm2, for interpolar away from 4cm, input current intensity is 2.0A.The initial COD concentration of reverse osmosis concentrated water is 2200mg/ L, volume 1.0L, initial pH6.6, reaction carry out 2h, and COD removal rate reaches 73%.
Embodiment 3：
A kind of to mix ceria and the co-modified ti-lead dioxide anode of bait, preparation method is as follows：By 50*20cm*3mm Clear water rinses after titanium mesh plate is polished with sand paper, then 80 DEG C of heating oil removing 2h in 40% sodium hydroxide solution again, after clear water is clean Ebuillition of heated 2-3h in 10% oxalic acid solution again, until grey pitted skin occurs in web plate surface, clear water is rinsed well.
Tin tetrachloride and antimony trichloride are dissolved in the isopropanol containing hydrochloric acid, and are coated on titanium plate matrix surface, 20min is roasted at 500 DEG C again after drying 10min at 120 DEG C, 10 times repeatedly, finally 2h is roasted at 500 DEG C, is had The group of the electrode of tin-antimony oxide bottom, tin tetrachloride and antimony trichloride coating liquid becomes the SnCl of 500mmol/L4·5H2O、 The SbCl of 60mmol/L3, isopropanol 100mL, concentrated hydrochloric acid 5mL.
Using the electrode with tin-antimony oxide bottom as anode, titanium plate is cathode, is plated in the sodium hydroxide dissolved with PbO Electro-deposition α-PbO in liquid2Middle layer, PbO sodium hydroxide plating solution group become 0.10mol/LPbO and 140g/L sodium hydroxide, deposition Time is 1.0h, and depositing temperature is 35 DEG C, and the current density of electro-deposition is 20mA/cm2, with about 400 revs/min in electrodeposition process The stirring of clock rate degree, pole plate spacing 1.5cm.
Titanium plate by above step preparation is anode, and titanium plate is cathode, is contained in the acidity of doping cerium dioxide and nitric acid bait In fluorine lead solution, the group of the fluorine-containing lead plating solution of the acidity containing ceria and nitric acid bait becomes the Pb (NO of 0.5mol/L3)2、 The HNO of 0.15mol/L3, 0.012mol/L NaF, 1.8g/L CeO2And Er (the NO of 0.05g/L3)3, electro-deposition, which is made, contains two Cerium oxide, bait, fluorine modification β-PbO2Active layer, electrodeposition time 1.5h, depositing temperature are 50 DEG C, electro-deposition current density For 35-45mA/cm2, stirred with about 500 revs/min of speed in electrodeposition process, pole plate spacing 4cm is to get to mixing ceria The co-modified ti-lead dioxide anode with bait.
Using this electrode plate as anode, stainless steel plate as cathode, certain factory's reverse osmosis concentrated water, annode area and yin are handled Pole-face product is 100cm2, for interpolar away from 4cm, input current intensity is 2.0A.The initial COD concentration of reverse osmosis concentrated water is 2200mg/ L, volume 1.0L, initial pH6.6, reaction carry out 2h, and COD removal rate reaches 70%.

Claims (9)

1. a kind of preparation method of ti-lead dioxide anode, it is characterised in that：Include the following steps：
1) titanium-based matrix is pre-processed, to remove matrix surface impurity and obtain the good surface of process performance；
2) tin tetrachloride and antimony trichloride are dissolved in the isopropanol containing hydrochloric acid, and are coated on titanium plate matrix surface, 120 5-20min is roasted again after drying 10-15min at DEG C, 8-10 times repeatedly, finally roasts 1.0-2.0h, obtains aoxidizing with tin antimony The electrode of object bottom；
3) using the electrode with tin-antimony oxide bottom as anode, titanium plate is cathode, in the sodium hydroxide plating solution for being dissolved with PbO Middle electro-deposition α-PbO2Middle layer；
It 4) is anode by the titanium plate of step (3) preparation, titanium plate is cathode, in the fluorine-containing lead of the acidity of doping cerium dioxide and nitric acid bait In solution, the group of the fluorine-containing lead plating solution of the acidity containing ceria and nitric acid bait becomes Pb (NO3)2、HNO3、NaF、CeO2And Er (NO3)3, electro-deposition be made containing ceria, bait, fluorine modification β-PbO2Active layer obtains the ti-lead dioxide anode.
2. preparation method described in accordance with the claim 1, it is characterised in that：The pretreatment packet that titanium-based matrix is carried out in step 1) Include polishing and decontamination.
3. preparation method according to claim 2, it is characterised in that：The pretreatment further includes acid etch processing.
4. preparation method described in accordance with the claim 1, it is characterised in that：Maturing temperature is 500 DEG C in the step 2).
5. preparation method described in accordance with the claim 1, it is characterised in that：Tin tetrachloride and antimony trichloride are molten in the step 2) Xie Yu contains in the isopropanol of hydrochloric acid in solution obtained, and the group of tin tetrachloride and antimony trichloride coating liquid becomes 500mmol/ The SnCl of L4·5H2O, the SbCl of 60 mmol/L3, the volume ratio of isopropanol and concentrated hydrochloric acid is 20:1-20:10.
6. preparation method described in accordance with the claim 1, it is characterised in that：PbO sodium hydroxide plating solution group becomes in step 3) 0.10mol/LPbO and 140g/L sodium hydroxide.
7. preparation method described in accordance with the claim 1, it is characterised in that：Electro-deposition α-PbO in step 3)2The deposition of middle layer Time is 0.5-1.0h, and depositing temperature is 35-45 DEG C, and the current density of electro-deposition is 20mA/cm2, with about in electrodeposition process 300-500 revs/min of speed stirring, pole plate spacing 1.5-5cm.
8. preparation method described in accordance with the claim 1, it is characterised in that：The group of acid fluorine-containing lead plating solution becomes in step 4) The HNO of the Pb (NO3) 2 of 0.5mol/L, 0.15mol/L3, 0.012mol/L NaF, 1.8g/L CeO2 and 0.05g/L Er (NO3)3。
9. preparation method described in accordance with the claim 1, it is characterised in that：Electro-deposition described in step 4), which is made, contains titanium dioxide Cerium, bait, fluorine modification β-PbO2The electrodeposition time of active layer is 1.0-2.0h, and depositing temperature is 35-50 DEG C, electro-deposition electric current Density is 35-45mA/cm2, stirred with about 300-500 revs/min speed in electrodeposition process, pole plate spacing 1.5-5cm.
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Cited By (5)

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CN111943327A (en) * 2019-05-14 2020-11-17 宝山钢铁股份有限公司 Having RuO for acidic wastewater treatment2-IrO2Electrode material of intermediate layer and preparation method
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CN113562815A (en) * 2021-08-13 2021-10-29 安徽康菲尔检测科技有限公司 Preparation method of composite coating DSA electrode for water treatment and prepared composite coating DSA electrode
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