CN105776441A - Three-dimensional porous titanium substrate lead dioxide electrode as well as preparation method and application thereof - Google Patents
Three-dimensional porous titanium substrate lead dioxide electrode as well as preparation method and application thereof Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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- 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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- 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
- C02F1/467—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction
- C02F1/4672—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction by electrooxydation
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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- 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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- C02F2001/46138—Electrodes comprising a substrate and a coating
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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- C02F2101/00—Nature of the contaminant
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Abstract
The invention discloses a three-dimensional porous titanium substrate lead dioxide electrode which comprises a porous titanium substrate, wherein interlayers are arranged on two side surfaces of the porous titanium substrate in a thermal deposition manner; the interlayers consists of a tin-antimony oxide; a lead dioxide surface active layer is arranged on the interlayer on one side surface of the porous titanium substrate in an electric deposition layer. The invention further provides a preparation method of the three-dimensional porous titanium substrate lead dioxide electrode, and further provides application of the three-dimensional porous titanium substrate lead dioxide electrode in musk ketone in degraded wastewater. In the musk ketone in the degraded wastewater, the three-dimensional porous titanium substrate lead dioxide electrode is taken as an anode, copper foil as a cathode and a sodium sulfate solution as an electrolyte, electrocatalytic oxidation is implemented for 1-2 hours, and then degradation treatment on the musk ketone in the wastewater can be completed. When the musk ketone is degraded by using the three-dimensional porous titanium substrate lead dioxide electrode under an electrifying condition, the degradation time is short, the degradation rate is high, and the operation is convenient.
Description
Technical field
The invention belongs to chemical field, relate to a kind of method for treating water, a kind of three-dimensional porous Titanium base lead dioxide electrode and its preparation method and application specifically.
Background technology
Along with the raising of people's living standard, the demand of medicine and personal care articles is increased, including various antibiotic, contraceptive, perfume, cosmetics, detergent and cleaning agent etc..Due to a large amount of uses of these compounds, to a certain extent surrounding is caused pollution, especially all detect in soil, water, air.Wherein sewage disposal plant effluent, human tissue cell all can detect the above-mentioned Organic substance completely that is not metabolized or degrades.Although the concentration level that these materials are in the environment many receiving g/l ~ micrograms per litre level between, but research shows that they enter in environment easily by various channels and are enriched with in ecological chain, and long-term existence in the environment, bringing potential hazard to whole ecosystem, they belong to typical persistency persistent organic pollutants.
Medicine and personal care articles exist a kind of material synthetic musk, artificial Moschus common in water body such as nitro class Moschus, many lopps Moschus etc. are all detected, and part synthetic musk can induce other toxicants to make its toxicity strengthen, destroy immunity and have carcinogenesis.The biologic treating technique simultaneously having bibliographical information traditional is difficult to degraded and removes this type organic, mostly by sludge absorption, then passes through other modes and is again introduced in environment to go to cause secondary pollution.
Discharge water after the wastewater treatment of countries in the world detects a large amount of persistency Recalcitrant chemicals matter, show that conventional waste water biochemical processing can not effectively meet the requirement of draining water quality, and the existing drinking water plant in various countries or waste water treatment plant are not specifically designed for difficult degradation organic micro-pollutants treatment technology.Therefore along with the requirement that people are higher to water quality safety, some are all badly in need of developing in current each state can more efficient, wastewater processing technology that expense is low, easy.Owing to advanced oxidation treatment technology has high efficiency, environmental friendliness, is prone to the advantages such as Automated condtrol, it will be the approach of a feasible degraded organic micro-pollutants.
At present, in degradation treatment waste water, the report of musk ketone is fewer, is used mostly activated sludge, ozone oxidation, light degradation and Fenton reagent method, but uses degradation time longer, and degradation efficiency is low, and some is also possible to produce secondary pollution degradation.And utilize three-dimensional porous Titanium base lead dioxide electrode by the method also rare report of high-level oxidation technology degraded musk ketone.
Three-dimensional porous Titanium base specific surface area is big, is conducive to Lead oxide brown active layer to be uniformly dispersed so that the current stabilization passed through, and reduces electric current density, improves the corrosion resistance of electrode, extends the service life of electrode.The advantages such as Lead oxide brown active layer has the satisfactory electrical conductivity similar with metal, also has higher overpotential for oxygen evolution, and corrosion resistance is strong, and catalysis activity is high, and hardness is big, cheap.So, three-dimensional porous Titanium base lead dioxide electrode is a kind of insoluble petal oxide anode material, has good electric conductivity and electro catalytic activity, and corrosion resistance is strong in acid, stability is high, is the electrode of a relatively high electrochemical performance.
Summary of the invention
For above-mentioned technical problem of the prior art, the invention provides a kind of three-dimensional porous Titanium base lead dioxide electrode and its preparation method and application and to solve the method time length of musk ketone in process waste water of the prior art, technical problem that degradation efficiency is low.
The invention provides a kind of three-dimensional porous Titanium base lead dioxide electrode, including a POROUS TITANIUM matrix, on two sides of described POROUS TITANIUM matrix, each heat deposition has an intermediate layer, described intermediate layer is made up of tin-antimony oxide, and intermediate layer, the side substrates at described POROUS TITANIUM PLATE matrix has Lead oxide brown surface activity layer.
The method that present invention also offers above-mentioned three-dimensional porous Titanium base lead dioxide electrode, comprises the steps:
1) step to porous titanio pretreatment, initially with machine glazed finish, removes POROUS TITANIUM electrode matrix oxide on surface and impurity, then uses sand papering corner, so as to round and smooth, finally rinse well with deionized water；Secondly being immersed in sodium hydroxide washing liquid by whole POROUS TITANIUM electrode, keep each pole piece to be in released state, heating is to 55 DEG C ~ 85 DEG C, and constant temperature keeps 35 minutes ~ 55 minutes, stops heating, cooling, rinses well with deionized water；Then whole POROUS TITANIUM electrode is immersed in hydrochloric acid lotion, processes 35 minutes ~ 55 minutes at 95 DEG C ~ 100 DEG C, use deionized water rinsing surface impurity, finally ultrasonic cleaning 25 minutes ~ 45 minutes in ultra-pure water, be subsequently placed in deionized water or isopropanol and preserve；
2) step preparing tin-antimony oxide intermediate layer, by stannic chloride pentahydrate, Butter of antimony. and concentrated hydrochloric acid are dissolved in isopropanol or n-butyl alcohol, described stannic chloride pentahydrate, Butter of antimony., concentrated hydrochloric acid, the mass volume ratio of isopropanol or n-butyl alcohol is 6.3 grams ~ 12.8 grams: 0.2 gram ~ 1.2 grams, 0.57 milliliter ~ 2 milliliters: 27 milliliters ~ 64 milliliters, it is configured to precursor solution, precursor solution is coated on the POROUS TITANIUM PLATE matrix after step 1) processes, dry at 100 DEG C ~ 130 DEG C, again the POROUS TITANIUM matrix of drying is placed in Muffle furnace 455 DEG C ~ 535 DEG C at roasting 8 minutes ~ 22 minutes, so 11 to 16 times repeatedly, in Muffle furnace, roasting time is 0.7 hour ~ 1.4 hours for the last time, naturally cool to room temperature；
3) step preparing Lead oxide brown active layer, using step 2) the POROUS TITANIUM PLATE matrix in tin-antimony oxide intermediate layer prepared is as anode, the Copper Foil of homalographic is as negative electrode, Lead oxide brown surface activity layer is prepared in electro-deposition in dissolved with the electroplate liquid of plumbi nitras, the electric current density of electro-deposition be 15 milliampere/square li ~ 45 milliampere/square centimeter, depositing temperature is 45 ~ 75 DEG C, and sedimentation time is 0.5 hour ~ 2 hours, obtains three-dimensional porous Titanium base lead dioxide electrode.
Further, the mass percent concentration of described sodium hydroxide washing liquid is 8% ~ 35%.
Further, the volume fraction of described hydrochloric acid lotion is 10% ~ 30%.
Further, electroplate liquid described in step 3) is made up of plumbi nitras, sodium fluoride, nitric acid and water, in described electroplate liquid, the concentration of plumbi nitras is 0.1 mol/L ~ 1.0 mol/L, the concentration of described sodium fluoride is 0.01 mol/L ~ 0.08 mol/L, and the concentration of described nitric acid is 0.02 mol/L ~ 0.35 mol/L.
Present invention also offers and adopt above-mentioned three-dimensional porous Titanium base lead dioxide electrode application in musk ketone in degrading waste water.
Further, application described above, in the waste water containing musk ketone, with three-dimensional porous Titanium base lead dioxide electrode for anode, Copper Foil is negative electrode, using the metabisulfite solution of 0.05 ~ 0.7 mol/L as electrolyte, electrocatalytic oxidation electric current density be 20 milliampere/square centimeter ~ 40 milliampere/square centimeter, after 1 hour ~ 2 hours, namely complete the degradation treatment of musk ketone in waste water.
The three-dimensional porous Titanium base lead dioxide electrode (Ti/SnO of the present invention2-Sb2O3/PbO2) it is with POROUS TITANIUM PLATE for matrix, after POROUS TITANIUM PLATE matrix is carried out surface preparation, heat deposition obtains SnO2-Sb2O3Intermediate layer, preparation Lead oxide brown electrodeposit liquid carries out electro-deposition and prepares three-dimensional porous Titanium base lead dioxide electrode.
Three-dimensional porous Titanium base lead dioxide electrode prepared by the present invention is using POROUS TITANIUM PLATE as matrix, and Lead oxide brown deposition layer is surface activity layer.The lead dioxide electrode that the present invention is matrix with POROUS TITANIUM, the titanium electrode material of preparation has active, the good mass transfer effect of excellent catalysis and longer service life, is a kind of high-performance, highly active lead dioxide electrode.
The present invention compares with prior art, and its technological progress is significant.The present invention changes tradition and prepares anode material with flat board titanium plate for matrix, adopts three-dimensional porous titanium to do matrix to prepare electrode.Novel lead dioxide electrode material prepared by the present invention declines in power on condition and solves musk ketone, has the advantages such as efficient degradation rate, environmental protection, reaction process simple and easy to control.The electro catalytic activity of organic wastewater is high, degradation time is short, degradation rate height, long service life, preparation technology is simple, easy to operate, cost is low, high financial profit.
Accompanying drawing explanation
Fig. 1 is musk ketone canonical plotting.
Fig. 2 is porous and the scanning electron microscope (SEM) photograph of each layer of flat board Titanium base lead dioxide electrode, and wherein figure a is the scanning electron microscope (SEM) photograph of POROUS TITANIUM matrix, and figure b is the scanning electron microscope (SEM) photograph of flat board Titanium base, and figure c is porous Ti intermediate layer SnO2-Sb2O3Scanning electron microscope (SEM) photograph, figure d be flat board Ti intermediate layer SnO2-Sb2O3Scanning electron microscope (SEM) photograph, figure e be porous Ti active layer PbO2Scanning electron microscope (SEM) photograph, figure f be flat board Ti active layer PbO2Scanning electron microscope (SEM) photograph.
Fig. 3 is POROUS TITANIUM matrix lead dioxide electrode of the present invention and the comparison diagram of flat board Titanium base lead dioxide electrode degraded musk ketone degradation efficiency.
Detailed description of the invention
Below by specific embodiment and in conjunction with accompanying drawing, the present invention is expanded on further, but is not limiting as the present invention.
Concentration is the musk ketone simulated wastewater of 0.5 mg/litre, and by every liter of calculating, its composition and content are as follows: methanol 276.5 mg/litre, phosphoric acid 0.175 mg/litre, musk ketone 0.5 mg/litre, surplus is water；
Musk ketone is with methanol: water: phosphate (TEDIA phosphoric acid, hour PLC/ chromatographic grade, purity is more than 99%)=60:40:0.3 makes solvent, is configured to the musk ketone simulated wastewater contrast degraded that concentration is 0.5 mg/litre, 5 mg/litre, 50 mg/litre, 100 mg/litre, 150 mg/litre respectively.
Embodiment 1
A kind of method utilizing the degraded of flat board Titanium base lead dioxide electrode to contain musk ketone waste water, specific implementation method is as follows:
(1) initially with machine glazed finish, remove electrode matrix oxide on surface and impurity, then use sand papering corner, so as to round and smooth, finally rinse well with deionized water；Secondly being immersed in sodium hydroxide washing liquid by whole electrode, keep each pole piece to be in released state, heating is to 55 DEG C ~ 85 DEG C, and constant temperature keeps 35 minutes ~ 55 minutes, stops heating, cooling, rinses well with deionized water；Then whole electrode is immersed in hydrochloric acid lotion, process 35 minutes ~ 55 minutes at 95 DEG C ~ 100 DEG C, use deionized water rinsing surface impurity, finally in ultra-pure water, ultrasonic cleaning is placed in deionized water or isopropanol for 25 minutes ~ 45 minutes and preserves, in the scanning electron microscope (SEM) photograph such as Fig. 2 on pretreatment rear plate Titanium base surface shown in b；
(2) by stannic chloride pentahydrate and Butter of antimony., concentrated hydrochloric acid is dissolved in isopropanol or n-butyl alcohol, described stannic chloride pentahydrate and Butter of antimony., concentrated hydrochloric acid, the mass volume ratio of isopropanol or n-butyl alcohol is 6.3 grams ~ 12.8 grams: 0.2 gram ~ 1.2 grams, 0.57 milliliter ~ 2 milliliters: 27 milliliters ~ 64 milliliters, it is configured to precursor solution, precursor solution is coated on the POROUS TITANIUM PLATE matrix after step 1) processes, dry at 100 DEG C ~ 130 DEG C in air dry oven, again the POROUS TITANIUM matrix of drying is placed in Muffle furnace 455 DEG C ~ 535 DEG C at roasting 8 minutes ~ 22 minutes, so 11 to 16 times repeatedly, in Muffle furnace, roasting time is 0.7 hour ~ 1.4 hours for the last time, naturally cool to room temperature, the flat board Ti electrode SnO prepared2-Sb2O3In interlayer surfaces scanning electron microscope (SEM) photograph such as Fig. 2 shown in d；
(3) flat board Ti/SnO2-Sb2O3As anode, the Copper Foil of homalographic is as negative electrode, die opening is 1.5 centimetres, Lead oxide brown active layer is prepared in electro-deposition in dissolved with the electroplate liquid of plumbi nitras, the electric current density of electro-deposition be 15 milliampere/square centimeter ~ 45 milliampere/square centimeter, depositing temperature is 45 DEG C ~ 75 DEG C, and sedimentation time is 0.5 hour ~ 2 hours, in the Lead oxide brown active layer surface scan Electronic Speculum figure such as Fig. 2 of the flat board Ti electrode prepared shown in f.
Further, the mass percent concentration of described sodium hydroxide solution is 8% ~ 35%.
Further, described hydrochloric acid lotion is volume fraction is the hydrochloric acid solution of 10% ~ 30%.
Further, plating solution described in step 3) is made up of plumbi nitras, sodium fluoride, nitric acid and water, the concentration of plumbi nitras is 0.1 mol/L ~ 1.0 mol/L, and the concentration of sodium fluoride is 0.01 mol/L ~ 0.08 mol/L, and the concentration of nitric acid is 0.02 mol/L ~ 0.35 mol/L.
Utilize external standard method, compound concentration is 0.5 mg/litre respectively, 5 mg/litre, 50 mg/litre, 100 mg/litre, the musk ketone standard solution of 150 mg/litre, detects the peak area of musk ketone, then with musk ketone concentration for abscissa by high performance liquid chromatography, draw with corresponding peak area for vertical coordinate, result is as it is shown in figure 1, from figure 1 it appears that the musk ketone standard curve equation of matching is:
Y=10494.06x+11739.15, R2=0.9992;
Wherein:
High performance liquid chromatography: chromatographic column is KromasilC18 (250 millimeters × 4.6 millimeters × 5 microns);
Variable-wavelenght detector, detects wavelength 235 nanometers;
Mobile phase: methanol/water/phosphate buffer calculates by volume, i.e. methanol: water: phosphate buffer is 60:40:0.3;
Flow velocity 1.0 ml/min;
Column temperature 35 DEG C;
Sample size 25 microlitre；
(4) the musk ketone simulated wastewater that concentration is 0.5 mg/litre of electrocatalytic oxidation 50 milliliters, the metabisulfite solution of 0.05 ~ 0.7 mol/L does supporting electrolyte, and the volume of solution is 70 milliliters, electrocatalytic oxidation electric current density be 20 milliampere/square centimeter ~ 40 milliampere/square centimeter, temperature is 25 DEG C ~ 35 DEG C, react 2 hours, reacting 0 minute, 10 minutes, 30 minutes, 60 minutes, 90 minutes, when 120 minutes, respectively take a sample.
(5) sample taken by step (4) different time, what the laggard liquid phase of ultrasound filtration measured the Moschus under different time goes out peak area, then passes through the standard curve of step (3) gained, calculates the concentration of musk ketone corresponding under the corresponding response time.Concentration according to musk ketone corresponding under the above-mentioned corresponding response time, calculate the degradation rate of musk ketone corresponding under the corresponding response time, then with the electrochemical degradation time for abscissa, with degradation rate for vertical coordinate, obtain flat board Titanium base lead dioxide electrode degraded musk ketone curve, as it is shown on figure 3, it appeared that, the degradation rate adopting flat board ti-supported lead dioxide electric pole degraded musk ketone after 1 hour only reaches about 60%, still fails all to remove after 2 hours.
Embodiment 2
A kind of method utilizing the degraded of three-dimensional porous Titanium base lead dioxide electrode to contain musk ketone waste water, specific implementation method is as follows:
(1) initially with machine glazed finish, remove electrode matrix oxide on surface and impurity, then use sand papering corner, so as to round and smooth, finally rinse well with deionized water；Secondly being immersed in sodium hydroxide washing liquid by whole electrode, keep each pole piece to be in released state, heating is to 55 DEG C ~ 85 DEG C, and constant temperature keeps 35 minutes ~ 55 minutes, stops heating, cooling, rinses well with deionized water；Then whole electrode is immersed in hydrochloric acid lotion, process 25 minutes ~ 45 minutes at 95 DEG C ~ 100 DEG C, use deionized water rinsing surface impurity, finally in ultra-pure water, ultrasonic cleaning is placed in deionized water or isopropanol for 25 minutes ~ 45 minutes and preserves, in scanning electron microscope (SEM) photograph such as Fig. 2 of pretreated POROUS TITANIUM matrix surface shown in a；
(2) by stannic chloride pentahydrate and Butter of antimony., concentrated hydrochloric acid is dissolved in isopropanol or n-butyl alcohol, described stannic chloride pentahydrate and Butter of antimony., concentrated hydrochloric acid, the mass volume ratio of isopropanol or n-butyl alcohol is 6.3 grams ~ 12.8 grams: 0.2 gram ~ 1.2 grams, 0.57 milliliter ~ 2 milliliters: 27 milliliters ~ 64 milliliters, it is configured to precursor solution, precursor solution is coated on the POROUS TITANIUM PLATE matrix after step 1) processes, dry at 100 DEG C ~ 130 DEG C in air dry oven, again the POROUS TITANIUM matrix of drying is placed in Muffle furnace 455 DEG C ~ 535 DEG C at roasting 8 minutes ~ 22 minutes, so 11 times to 16 times repeatedly, in Muffle furnace, roasting time is 0.7 hour ~ 1.4 hours for the last time, naturally cool to room temperature, the POROUS TITANIUM electrode SnO prepared2-Sb2O3In interlayer surfaces scanning electron microscope (SEM) photograph such as Fig. 2 shown in c；
(3) porous Ti/SnO2~Sb2O3As anode, the Copper Foil of homalographic is as negative electrode, die opening is 1.5 centimetres, Lead oxide brown active layer is prepared in electro-deposition in dissolved with the electroplate liquid of plumbi nitras, the electric current density of electro-deposition be 15 milliampere/square centimeter ~ 45 milliampere/square centimeter, depositing temperature is 45 DEG C ~ 75 DEG C, and sedimentation time is 0.5 hour ~ 2 hours, in the Lead oxide brown active layer surface scan Electronic Speculum figure such as Fig. 2 of the POROUS TITANIUM electrode prepared shown in e.
Further, the mass percent concentration of described sodium hydroxide solution is 8% ~ 35%.
Further, described hydrochloric acid lotion is volume fraction is the hydrochloric acid solution of 10% ~ 30%.
Further, plating solution described in step 3) is made up of plumbi nitras, sodium fluoride, nitric acid and water, the concentration of plumbi nitras is 0.1 mol/L ~ 1.0 mol/L, and the concentration of sodium fluoride is 0.01 mol/L ~ 0.08 mol/L, and the concentration of nitric acid is 0.02 mol/L ~ 0.35 mol/L.
Utilize external standard method, compound concentration is 0.5 mg/litre respectively, 5 mg/litre, 50 mg/litre, 100 mg/litre, the musk ketone standard solution of 150 mg/litre, detects the peak area of musk ketone, then with musk ketone concentration for abscissa by high performance liquid chromatography, draw with corresponding peak area for vertical coordinate, result is as it is shown in figure 1, from figure 1 it appears that the musk ketone standard curve equation of matching is:
Y=10494.06x+11739.15, R2=0.9992;
Wherein:
High performance liquid chromatography: chromatographic column is KromasilC18 (250 millimeters × 4.6 millimeters × 5 microns);
Variable-wavelenght detector, detects wavelength 235 nanometers;
Mobile phase: methanol/water/phosphate buffer calculates by volume, i.e. methanol: water: phosphate buffer is 60:40:0.3;
Flow velocity 1.0 ml/min;
Column temperature 35 DEG C;
Sample size 25 microlitre；
(4) the musk ketone simulated wastewater that concentration is 0.5 mg/litre of electrocatalytic oxidation 50 milliliters, the metabisulfite solution of 0.05 ~ 0.7 mol/L does supporting electrolyte, and the volume of solution is 70 milliliters, electrocatalytic oxidation electric current density be 20 milliampere/square centimeter ~ 40 milliampere/square centimeter, temperature is 25 DEG C ~ 35 DEG C, react 2 hours, reacting 0 minute, 10 minutes, 30 minutes, 60 minutes, 90 minutes, when 120 minutes, respectively take a sample.
(5) sample that step (4) different time is taken, what the laggard liquid phase of ultrasound filtration measured the Moschus under different time goes out peak area, then pass through the standard curve of step (3) gained, calculate the concentration of musk ketone corresponding under the corresponding response time.Concentration according to musk ketone corresponding under the above-mentioned corresponding response time, calculate the degradation rate of musk ketone corresponding under the corresponding response time, then with the electrochemical degradation time for abscissa, with degradation rate for vertical coordinate, obtain POROUS TITANIUM matrix lead dioxide electrode degraded musk ketone curve, as it is shown on figure 3, it appeared that, the degradation rate adopting POROUS TITANIUM base lead dioxide electrode degraded musk ketone after 1 hour has reached about 90%, substantially all removal after 2 hours.
Contrast by the above embodiments 1 and embodiment 2, can be seen that, a kind of POROUS TITANIUM matrix lead dioxide electrode of the present invention is better than the effect of the degraded of classic flat-plate Titanium base lead dioxide electrode degraded muscone, under identical degradation time, its degradation rate improves 30%, and can be degradable by muscone after certain time.
Above example is merely to illustrate the present invention rather than restriction the scope of the present invention.Additionally, after having read the content that the present invention lectures, the present invention can be made various changes or modifications by those skilled in the art, and these equivalent form of values fall within the application appended claims limited range equally.
Claims (7)
1. a three-dimensional porous Titanium base lead dioxide electrode, including a POROUS TITANIUM matrix, on two sides of described POROUS TITANIUM matrix, each heat deposition has an intermediate layer, described intermediate layer is made up of tin-antimony oxide, and intermediate layer, the side substrates at described POROUS TITANIUM PLATE matrix has Lead oxide brown surface activity layer.
2. the method for a kind of three-dimensional porous Titanium base lead dioxide electrode described in claim 1, comprises the steps:
1) step to porous titanio pretreatment, initially with machine glazed finish, removes POROUS TITANIUM electrode matrix oxide on surface and impurity, then uses sand papering corner, so as to round and smooth, finally rinse well with deionized water；Secondly being immersed in sodium hydroxide washing liquid by whole POROUS TITANIUM electrode, keep each pole piece to be in released state, heating is to 55 DEG C ~ 85 DEG C, and constant temperature keeps 35 minutes ~ 55 minutes, stops heating, cooling, rinses well with deionized water；Then whole POROUS TITANIUM electrode is immersed in hydrochloric acid lotion, processes 35 minutes ~ 55 minutes at 95 DEG C ~ 100 DEG C, use deionized water rinsing surface impurity, finally ultrasonic cleaning 25 minutes ~ 45 minutes in ultra-pure water, be subsequently placed in deionized water or isopropanol and preserve；
2) step preparing tin-antimony oxide intermediate layer, by stannic chloride pentahydrate, Butter of antimony. and concentrated hydrochloric acid are dissolved in isopropanol or n-butyl alcohol, described stannic chloride pentahydrate, Butter of antimony., concentrated hydrochloric acid, the mass volume ratio of isopropanol or n-butyl alcohol is 6.3 grams ~ 12.8 grams: 0.2 gram ~ 1.2 grams, 0.57 milliliter ~ 2 milliliters: 27 milliliters ~ 64 milliliters, it is configured to precursor solution, precursor solution is coated on the POROUS TITANIUM PLATE matrix after step 1) processes, dry at 100 DEG C ~ 130 DEG C, again the POROUS TITANIUM matrix of drying is placed in Muffle furnace, roasting 8 minutes ~ 22 minutes at 455 DEG C ~ 535 DEG C, so 11 to 16 times repeatedly, in Muffle furnace, roasting time is 0.7 hour ~ 1.4 hours for the last time, naturally cool to room temperature；
3) step preparing Lead oxide brown active layer, using step 2) the POROUS TITANIUM PLATE matrix in tin-antimony oxide intermediate layer prepared is as anode, the Copper Foil of homalographic is as negative electrode, Lead oxide brown surface activity layer is prepared in electro-deposition in dissolved with the electroplate liquid of plumbi nitras, the electric current density of electro-deposition be 15 milliampere/square centimeter ~ 45 milliampere/square centimeter, depositing temperature is 45 ~ 75 DEG C, and sedimentation time is 0.5 hour ~ 2 hours, obtains three-dimensional porous Titanium base lead dioxide electrode.
3. the method for a kind of three-dimensional porous Titanium base lead dioxide electrode according to claim 2, it is characterised in that: the mass percent concentration of described sodium hydroxide washing liquid is 8% ~ 35%.
4. the method for a kind of three-dimensional porous Titanium base lead dioxide electrode according to claim 2, it is characterised in that: the volume fraction of described hydrochloric acid lotion is 10% ~ 30%.
5. the method for a kind of three-dimensional porous Titanium base lead dioxide electrode according to claim 2, it is characterized in that: the electroplate liquid described in step 3) is made up of plumbi nitras, sodium fluoride, nitric acid and water, in described electroplate liquid, the concentration of plumbi nitras is 0.1 mol/L ~ 1.0 mol/L, the concentration of described sodium fluoride is 0.01 mol/L ~ 0.08 mol/L, and the concentration of described nitric acid is 0.02 mol/L ~ 0.35 mol/L.
6. the application in the musk ketone in degrading waste water of the three-dimensional porous Titanium base lead dioxide electrode described in claim 1.
7. application according to claim 6, it is characterized in that: in the waste water containing musk ketone, with three-dimensional porous Titanium base lead dioxide electrode for anode, Copper Foil is negative electrode, using the metabisulfite solution of 0.05 mol/L ~ 0.7 mol/L as electrolyte, electrocatalytic oxidation electric current density be 20 milliampere/square centimeter ~ 40 milliampere/square centimeter, after 1 hour ~ 2 hours, namely complete the degradation treatment of musk ketone in waste water.
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| CN109095567A (en) * | 2018-08-17 | 2018-12-28 | 广东工业大学 | A kind of carbon paper substrate lead dioxide electrode and its preparation method and application |
| CN110217861A (en) * | 2019-06-06 | 2019-09-10 | 西安建筑科技大学 | A kind of preparation and application of long-life porous ti-supported lead dioxide electric pole material |
| CN110330078A (en) * | 2019-06-28 | 2019-10-15 | 浙江大学 | A kind of three-dimensional structure antimony-doped tin oxide electrode of efficient and long life |
| 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 |
| CN111675289A (en) * | 2020-06-28 | 2020-09-18 | 盐城工学院 | Preparation method of porous titanium-based lead dioxide electrode |
| CN111962121A (en) * | 2020-08-19 | 2020-11-20 | 西安交通大学 | Method for quickly constructing titanium substrate three-dimensional porous lead dioxide active layer |
| CN112095118A (en) * | 2020-09-03 | 2020-12-18 | 广东臻鼎环境科技有限公司 | Composite lead dioxide anode and preparation method thereof |
| CN114751489A (en) * | 2022-05-11 | 2022-07-15 | 昆明理工大学 | Gradient porous titanium-based/lead dioxide composite electrode and preparation method thereof |
| CN114933349A (en) * | 2022-05-16 | 2022-08-23 | 桂林电子科技大学 | Titanium-based metal oxide coating filtering membrane, preparation method and application thereof, coupling reactor and sewage treatment method |
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| CN109095567A (en) * | 2018-08-17 | 2018-12-28 | 广东工业大学 | A kind of carbon paper substrate lead dioxide electrode and its preparation method and application |
| CN110217861B (en) * | 2019-06-06 | 2021-11-02 | 西安建筑科技大学 | Preparation and application of long-life porous titanium-based lead dioxide electrode material |
| CN110217861A (en) * | 2019-06-06 | 2019-09-10 | 西安建筑科技大学 | A kind of preparation and application of long-life porous ti-supported lead dioxide electric pole material |
| CN110330078A (en) * | 2019-06-28 | 2019-10-15 | 浙江大学 | A kind of three-dimensional structure antimony-doped tin oxide electrode of efficient and long life |
| CN110330078B (en) * | 2019-06-28 | 2020-09-15 | 浙江大学 | High-efficiency long-life three-dimensional structure antimony-doped tin oxide 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 |
| CN111675289A (en) * | 2020-06-28 | 2020-09-18 | 盐城工学院 | Preparation method of porous titanium-based lead dioxide electrode |
| CN111962121A (en) * | 2020-08-19 | 2020-11-20 | 西安交通大学 | Method for quickly constructing titanium substrate three-dimensional porous lead dioxide active layer |
| CN111962121B (en) * | 2020-08-19 | 2021-11-19 | 西安交通大学 | Method for quickly constructing titanium substrate three-dimensional porous lead dioxide active layer |
| CN112095118A (en) * | 2020-09-03 | 2020-12-18 | 广东臻鼎环境科技有限公司 | Composite lead dioxide anode and preparation method thereof |
| CN114751489A (en) * | 2022-05-11 | 2022-07-15 | 昆明理工大学 | Gradient porous titanium-based/lead dioxide composite electrode and preparation method thereof |
| CN114751489B (en) * | 2022-05-11 | 2024-03-19 | 昆明理工大学 | Gradient porous titanium-based/lead dioxide composite electrode and preparation method thereof |
| CN114933349A (en) * | 2022-05-16 | 2022-08-23 | 桂林电子科技大学 | Titanium-based metal oxide coating filtering membrane, preparation method and application thereof, coupling reactor and sewage treatment method |
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