CN102464382B - High oxygen evolution potential and electrode preparation method for treating fluorine containing organic waste water - Google Patents
High oxygen evolution potential and electrode preparation method for treating fluorine containing organic waste water Download PDFInfo
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Abstract
The invention relates to a high oxygen evolution potential and electrode preparation method for treating fluorine containing organic waste water. The method is characterized in that titanium matrix body titania nanotube array is prepared through an anodization treatment, a doped type SnO2-Sb2O5/TiO2-NTs electrode is prepared by using a pulse electrodeposition method, compared with Sb doped SnO2 electrode prepared by a traditional sol gel method, the SnO2-Sb2O5/TiO2-NTs electrode enables superhigh oxygen evolution potential which can reach as high as more than 2.4V, and has the advantages of high electrocatalytic activity, strong electrochemistry oxidation capability and high efficiency. According to the invention, fluorine containing aromatic hydrocarbon organic pollutants with difficult biochemistry and difficult oxidation can be degraded with high efficiency by the electrode through the electrochemistry oxidation method, the high oxygen evolution potential and electrode preparation method for treating fluorine containing organic waste water has wide economic and social benefit.
Description
Technical field
The present invention relates to the materials chemistry field, especially relate to a kind of preparation method who processes the oxygen evolution potential electrode of fluorine containing organic waste water.
Background technology
The principle of electrochemical oxidation method is the main oxygenant of hydroxyl radical free radical (OH) conduct that produces by anode, utilizes the strong oxidizing property of hydroxyl radical free radical that organic pollutant is degraded to organic molecule intermediate or CO
2Electrochemical oxidation process consumes chemical reagent hardly, and the secondary pollution of generation is few, is called as the environmental friendliness technology.In addition, electrochemical oxidation method also has the advantages such as oxidation capacity is strong, controllability is high, reaction conditions is gentle, floor space is little, is efficient environmental pollutant degradation technique, is subject to increasing attention, and application prospect is very extensive.And maximum effect factor that limits this technical development is anode material.Anode material except be prepared into should be cheap as much as possible, also must possess good electroconductibility, high oxygen evolution potential and the good characteristics such as catalyzed degradation activity, to be applied to the electrochemicial oxidation of Organic Pollutants in Wastewater.
Investigation of titanium anode coated with metal oxide is the anode material that a class is applicable to the Organic Pollutants in Wastewater electrochemicial oxidation, has caused widely to pay close attention to.Wherein mix the SnO of antimony
2Be a kind of good eelctro-catalyst, have higher oxygen evolution potential and electro catalytic activity preferably, be applicable to the By Electro-catalytic Oxidation Process of organic pollutant, become the focus of research.The people such as Stucki utilize cladding process to prepare the titanium-matrix electrode of the tindioxide of antimony dopant, and its oxygen evolution potential reaches more than the 1.8V vs SCE.With PbO
2, the Pt electrode is compared, SnO
2Electrode pair phenol, benzoic oxidation efficiency is higher, is the better electrode of a class.The people such as Comninellis have investigated the SnO of antimony dopant
2The chemical property of titanium-matrix electrode, research is found, with some traditional Pt electrode and RuO
2, IrO
2Titanium-matrix electrode is compared, the SnO of doping Sb
2Electrode not only preparation cost is relatively cheap, and will be higher than above-mentioned electrode to the degradation efficiency as pollutents such as phenol, benzoquinones and aromatic amine, ammonia nitrogens.The toxicity intermediate product that this electrode pair reactant and reaction process produce has good catalytic performance, thereby can obtain faster, more thoroughly oxidation, and intermediate product is few, is the more efficient anode material of a class.The people such as Grmim adopt sol-gel method to prepare the SnO2/Ti electrode, and have studied the catalytic oxidation behavior of phenol on this electrode.The result shows that the SnO2/Ti electrode can suppress oxygen evolution reaction effectively because oxygen evolution potential is higher, and the degradation efficiency of phenol is improved.In addition, mix the SnO of antimony
2Eelctro-catalyst is easy to preparation, and is with low cost.Mix just the SnO of antimony
2Therefore electrode possesses above-mentioned many merits, is considered to be applied in the electrochemicial oxidation technology of organic pollutant wastewater, has one of electrode of development potentiality.
But, although traditional method, such as sol-gel method, electrodip process etc., the SnO that mixes antimony of preparation
2Electrode has higher oxygen evolution potential and stronger catalytic oxidation ability, but compare with another kind of efficiently anode material boron-doped diamond film (BDD) electrode of developing in recent years, the latter shows more excellent electrochemical degradation ability and degradation rate faster.This mainly is because the BDD electrode has higher oxygen evolution potential, reaches more than the 2.4V.Therefore, utilize simple electro-deposition method, by to SnO
2Electrode carries out structure design and surface doping modification, when improving its good electric catalytic performance, further improve its oxygen evolution potential, will certainly obtain a kind of novel electrode with excellent electrochemical catalytic oxidation performance, have great significance for research and the application of the electrocatalytic oxidation method of organic pollutant.
Summary of the invention
Purpose of the present invention is exactly the preparation method that a kind of oxygen evolution potential electrode of the processing fluorine containing organic waste water that has superelevation oxygen evolution potential and high catalytic activity concurrently is provided in order to overcome the defective that above-mentioned prior art exists.
Purpose of the present invention can be achieved through the following technical solutions:
A kind of preparation method who processes the oxygen evolution potential electrode of fluorine containing organic waste water is characterized in that, the method adopts the pulse electrodeposition method to prepare doping type SnO on the Nano tube array of titanium dioxide matrix for preparing through anodizing
2-Sb
2O
5/ TiO
2-NTs electrode is product.
The method specifically may further comprise the steps:
(1) the pure metal titanium plate surface is carried out sanding and polishing with abrasive paper for metallograph, containing the NH of 0.05～1.0wt%
4F, the Na of 1.6～2.0wt%
2SO
4And 10～50wt% molecular weight be in the solution of 400 polyoxyethylene glycol take this titanium sheet as working electrode, platinized platinum is to electrode, carries out electrochemical anodic oxidation and processes, and obtains orderly TiO at titanium-based surface
2Nanometer pipe array electrode TiO
2-NTs adopts temperature programming to heat-treat in tube furnace at the electrode for preparing;
(2) with SnCl
22H
2O, SbCl
3, oxyethyl group aminopropyl trisiloxane tensio-active agent and hydrochloric acid is mixed with electroplate liquid, SnCl in this electroplate liquid
2Concentration be 0.2～0.5mol/L, SbCl
3Concentration be 0.2～0.4mol/L, the concentration of hydrochloric acid is 2～3mol/L, the concentration of oxyethyl group aminopropyl trisiloxane tensio-active agent is 0.2～0.3g/L;
(3) TiO for preparing with step (1)
2-NTs is working electrode, and platinized platinum is to electrode, and saturated calomel electrode is reference electrode, at 1～2mol L
-1Ammonium chloride solution in, under 40 ℃ of conditions of temperature, under the current potential of-1.5V, reduce 3s, then adopt 1.5mol L
-1CuSO
4By the pulse electrodeposition method, the control temperature is 40 ℃ Cu is deposited to TiO as electrolytic solution
2The bottom of-NTs, depositing time are 5～10min, will deposit the TiO of Cu again
2The electroplate liquid that-NTs places step (2) to dispose adopts the pulse electrodeposition method, and the control depositing temperature is 40 ℃, and depositing time is 2～4h, with the SnO of doping Sb
2Deposit to TiO
2Among-the NTs, prepare oxygen evolution potential high catalytic activity SnO
2-Sb
2O
5/ TiO
2-NTs electrode is product.
Heat treated temperature programming speed is 1～5 ℃/min in the described step (1), and thermal treatment temp is 450～550 ℃, and heat treatment time is 3～5h.
In the described step (3) with CuSO
4The deposition cycle parameter of the pulse electrodeposition method that adopts during as electrolytic solution is-70mA, 10ms 70mA, 1ms, 0mA, 1s.
In the described step (3) with the SnO of doping Sb
2The deposition cycle parameter that deposits to the pulse electrodeposition method in the nanotube is 45mA, 10m
s,-45mA, 1ms, 0mA, 1s.
Compared with prior art, the present invention utilizes the method for pulse electrodeposition to SnO
2The coating surface structure is transformed, and obtains the Sb doping SnO with three-dimensional structure
2Decorative layer, the electrode of acquisition show very high oxygen evolution potential and electro catalytic activity and utilize the efficient electrochemical oxidation of this electrode dysoxidizable fluorine-containing aromatic hydrocarbons pollutant of degrading, and such as fluorobenzene, difluorobenzene etc., specifically comprise following advantage:
(1) with conventional Ti base SnO
2Anode is compared, and the present invention has adopted the orderly TiO that stands on the metal Ti base
2Nano-tube array is the base electrode material, this nano-tube array high-sequential, and physical and chemical performance is stable, and very large specific surface area and freeboard can be provided.Its porous pipe type structure more is conducive to SnO
2The load of catalyzer.Simultaneously, the upright TiO of growth in situ
2Nano-tube array preparation technology is easier, economical, and its plank frame can directly as being the catalysis electrode solid support material, need not to be coated on other carriers.
(2) the present invention utilizes better simply pulse electrodeposition, by conditions such as control technique, electroplate liquids, and the oxygen evolution potential of energy Effective Raise electrode, the simultaneously adding of oxyethyl group aminopropyl trisiloxane tensio-active agent makes electrode surface SnO
2Particulate presents microspheroidal, disperses more evenly closely to have improved structure and the character of electrode surface, has improved the electro catalytic activity of electrode.
(3) the present invention adopts to matrix prereduction and by the deposition of a small amount of metal Cu and improves the method for matrix electroconductibility, is conducive to SnO
2Combination with matrix.Employing pulsed current deposition, preparation technology is simple, and electrode is with low cost.
Description of drawings
Fig. 1 is the SnO of embodiment 1 preparation
2-Sb
2O
5/ TiO
2The stereoscan photograph of-NTs electrode;
The SnO of Fig. 2 embodiment 1 preparation
2-Sb
2O
5/ TiO
2The polarization curve of-NTs electrode in acidic medium;
Fig. 3 is the SnO of embodiment 1 preparation
2-Sb
2O
5/ TiO
2The alternating-current impedance figure of-NTs electrode in potassium ferricyanide solution;
The SnO of Fig. 4 embodiment 1 preparation
2-Sb
2O
5/ TiO
2The i-t curve of-NTs electrode in metabisulfite solution.
Embodiment
The present invention is described in detail below in conjunction with the drawings and specific embodiments.
A kind of preparation method who processes the oxygen evolution potential electrode of fluorine containing organic waste water specifically may further comprise the steps:
The pure titanium sheet (99%) of 0.80mm is used 100 successively
#, 300
#With 500
#Sand papering is further polished with abrasive paper for metallograph, makes matrix surface smooth, and then each ultrasonic cleaning 20min in distilled water and acetone cleans up with redistilled water.Anodizing electrolytic solution consists of 0.8wt%NaF, 2%wtNaSO
4, 10wt% polyoxyethylene glycol (400).Anodizing voltage is 20V, anodizing time 5h.Thermal treatment temp is 450 ℃, and the intensification rate of temperature fall is 1 ℃ of min
-1Prepare TiO
2-NTs.With 0.2mol L
-1SnCl
2, 0.3mol L
-1SbCl
3, 2molL
-1HCl and 0.3g L
-1Oxyethyl group aminopropyl trisiloxane tensio-active agent is mixed with electroplate liquid; With TiO
2-NTs is working electrode, and platinized platinum is supporting electrode, and saturated calomel electrode (SCE) is reference electrode, under 40 ℃ of temperature of reaction, adopts the pulsed current method the SnO of doping Sb
2Deposit to TiO
2On-the NTs, deposition parameter is (45mA, 10ms;-45mA, 1ms; 0mA, 1s), depositing time is 2h.Prepare oxygen evolution potential high catalytic activity SnO
2-Sb
2O
5/ TiO
2-NTs electrode.
The electrode surface pattern characterizes by field emission scanning electron microscope (SEM), sees Fig. 1, can find out that the tin-antimony oxide uniform particles is dispersed in TiO on scheming
2In-NTs the substrate, the tin-antimony oxide particle that forms after a large amount of depositions has formed certain microspheroidal structure, is uniformly dispersed, and particle is combined closely each other with particle, but does not reunite, and the gap is clear.Electrode surface presents the three-dimensional structure with gradation sense.
Adopt three-electrode electro Chemical to measure system, on the CHI660c electrochemical workstation, with the SnO for preparing
2-Sb
2O
5/ TiO
2-NTs electrode is working electrode, and platinum electrode is to electrode, and saturated calomel electrode (SCE) is reference electrode, at 0.1mol L
-1H
2SO
4Measure the anodic polarization curves of electrode in the solution, see Fig. 2, the oxygen evolution potential that can record electrode is about 2.43V.
With the SnO for preparing
2-Sb
2O
5/ TiO
2-NTs electrode is working electrode, and platinum electrode is to electrode, and saturated calomel electrode (SCE) is reference electrode, measures the resistance of electrode in the 5mmol/L potassium ferricyanide solution with AC impedence method, sees Fig. 3, and the alternating-current impedance that can record electrode is about 190 Ω.
With the SnO for preparing
2-Sb
2O
5/ TiO
2-NTs electrode is working electrode, and platinum electrode is to electrode, and saturated calomel electrode (SCE) is reference electrode, under the voltage conditions of 3V, utilizes the i-t method to study electrode at 0.1molL
-1Na
2SO
4Fig. 4 is seen in electrocatalysis in solution response, when at Na
2SO
4After splashing into a small amount of FB in the solution, the current density of electrode obviously increases, and amplification is up to 54.1%.
The SnO that employing prepares
2-Sb
2O
5/ TiO
2-NTs electrode By Electro-catalytic Oxidation Process weedicide 2,4 dichlorophenoxyacetic acid.
Electrocatalysis Degradation carries out in the circular electric chemical reaction pond of single pond, adds a set of cups with recirculated water, and the maintenance temperature of reaction system is room temperature.Take the preparation electrode as anode, the Ti plate is that electrode area is 4.5cm to electrode
2, electrochemical degradation adopts constant-current electrolysis, constant current density 20mA cm
-2To contain 0.1mol L
-1Na
2SO
4Electrolytical 100mg L
-1The weedicide 2,4 dichlorophenoxyacetic acid is as simulated wastewater, and reaction volume is 100ml, proceeds to different moment samplings in DeR and analyzes.The concentration of measuring 2,4 dichlorophenoxyacetic acid in the degradation process with HPLC over time.The total content of organic carbon of sample (TOC) adopts the TOC determinator to measure.The result shows that after electrochemical degradation was processed 2h, the density loss of 2,4 dichlorophenoxyacetic acid was 8.26mgL
-1, transformation efficiency reaches 91.7%; After electrochemical degradation was processed 3h, the transformation efficiency of TOC reached 85.5%.
The SnO that employing prepares
2-Sb
2O
5/ TiO
2-NTs electrode By Electro-catalytic Oxidation Process fluorobenzene.
Electrocatalysis Degradation carries out in the circular electric chemical reaction pond of single pond, reaction tank with add the circulating condensing system and be connected, prevent the volatilization of fluorobenzene in the reaction process.Take the preparation electrode as anode, the Ti plate is that electrode area is 4.5cm to electrode
2, adopt constant-current electrolysis to degrade, constant current density is 20mA cm
-2, to contain 0.1mol L
-1Na
2SO
4Electrolytical 50mg L
-1Fluorobenzene be simulated wastewater, reaction volume is 70ml, DeR proceed to different constantly the time sampling analyze.The concentration of measuring fluorobenzene in the degradation process with HPLC over time.The total content of organic carbon of sample (TOC) adopts the TOC determinator to measure.The result shows that after electrochemical degradation was processed 2h, the concentration of fluorobenzene almost dropped to 0, and transformation efficiency reaches 99.8%; After electrochemical degradation was processed 3h, the transformation efficiency of TOC reached 90.6%.And under the same conditions, utilize the SnO of traditional sol-gel method preparation
2Behind/Ti electrode electro Chemical degradation treatment fluorobenzene 2h and the 3h, the TOC transformation efficiency is respectively 25.5% and 34.3%.This shows the SnO of present method preparation
2-Sb
2O
5/ TiO
2-NTs electrode dysoxidizable fluorine-containing arene the pollutent of can degrading efficiently.
Above-mentioned examples prove: at TiO
2On the nano-tube array matrix, adopt simple pulse electrodeposition method, by the doping of metallic element Sb, can obtain to have simultaneously the SnO of superelevation oxygen evolution potential and high catalytic activity
2Electrode.This electrode can be used for the high-efficiency electrochemical degradation treatment of high concentrated organic wastewater.
Embodiment 4
A kind of preparation method who processes the oxygen evolution potential electrode of fluorine containing organic waste water on the Nano tube array of titanium dioxide matrix for preparing through anodizing, adopts the pulse electrodeposition method to prepare doping type SnO
2-Sb
2O
5/ TiO
2-NTs electrode specifically may further comprise the steps:
(1) the pure metal titanium plate surface is carried out sanding and polishing with abrasive paper for metallograph, containing the NH of 0.05wt%
4F, the Na of 1.6wt%
2SO
4And in the solution of the polyoxyethylene glycol of 10wt% (400) take the titanium sheet as working electrode, platinized platinum is to electrode, carries out electrochemical anodic oxidation and processes, and obtains orderly TiO at titanium-based surface
2Nanometer pipe array electrode TiO
2-NTs adopts temperature programming to heat-treat in tube furnace at the electrode for preparing, and heat treated temperature programming speed is 1 ℃/min, and thermal treatment temp is 450 ℃, and heat treatment time is 5h;
(2) with SnCl
22H
2O, SbCl
3, oxyethyl group aminopropyl trisiloxane tensio-active agent and hydrochloric acid is mixed with electroplate liquid, SnCl in this electroplate liquid
2Concentration be 0.2mol/L, SbCl
3Concentration be 0.2mol/L, the concentration of hydrochloric acid is 2mol/L, the concentration of oxyethyl group aminopropyl trisiloxane tensio-active agent is 0.2g/L;
(3) TiO for preparing with step (1)
2-NTs is working electrode, and platinized platinum is to electrode, and saturated calomel electrode is reference electrode, at 1mol L
-1Ammonium chloride solution in, under 40 ℃ of conditions of temperature, under the current potential of-1.5V, reduce 3s, then adopt 1.5mol L
-1CuSO
4By the pulse electrodeposition method, the control temperature is 40 ℃ Cu is deposited to the bottom of nanotube that depositing time is 5min as electrolytic solution, the deposition cycle parameter is-70mA, 10ms 70mA, 1ms, 0mA, 1s, to deposit again the electroplate liquid that the nanotube of Cu places step (2) to dispose, adopt the pulse electrodeposition method, the control depositing temperature is 40 ℃, and depositing time is 2h, the deposition cycle parameter is 45mA, 10ms,-45mA, 1ms, 0mA, 1s are with the SnO of doping Sb
2Deposit in the nanotube, prepare oxygen evolution potential high catalytic activity SnO
2-Sb
2O
5/ TiO
2-NTs electrode is product.
Embodiment 5
A kind of preparation method who processes the oxygen evolution potential electrode of fluorine containing organic waste water on the Nano tube array of titanium dioxide matrix for preparing through anodizing, adopts the pulse electrodeposition method to prepare doping type SnO
2-Sb
2O
5/ TiO
2-NTs electrode specifically may further comprise the steps:
(1) the pure metal titanium plate surface is carried out sanding and polishing with abrasive paper for metallograph, containing the NH of 1.0wt%
4F, the Na of 2.0wt%
2SO
4And in the solution of 50wt% polyoxyethylene glycol (400) take the titanium sheet as working electrode, platinized platinum is to electrode, carries out electrochemical anodic oxidation and processes, and obtains orderly TiO at titanium-based surface
2Nanometer pipe array electrode TiO
2-NTs adopts temperature programming to heat-treat in tube furnace at the electrode for preparing, and heat treated temperature programming speed is 5 ℃/min, and thermal treatment temp is 550 ℃, and heat treatment time is 3h;
(2) with SnCl
22H
2O, SbCl
3, oxyethyl group aminopropyl trisiloxane tensio-active agent and hydrochloric acid is mixed with electroplate liquid, SnCl in this electroplate liquid
2Concentration be 0.5mol/L, SbCl
3Concentration be 0.4mol/L, the concentration of hydrochloric acid is 3mol/L, the concentration of oxyethyl group aminopropyl trisiloxane tensio-active agent is 0.3g/L;
(3) TiO for preparing with step (1)
2-NTs is working electrode, and platinized platinum is to electrode, and saturated calomel electrode is reference electrode, at 2mol L
-1Ammonium chloride solution in, under 40 ℃ of conditions of temperature, under the current potential of-1.5V, reduce 3s, then adopt 1.5mol L
-1CuSO
4By the pulse electrodeposition method, the control temperature is 40 ℃ Cu is deposited to the bottom of nanotube that depositing time is 10min as electrolytic solution, the deposition cycle parameter is-70mA, 10ms 70mA, 1ms, 0mA, 1s, to deposit again the electroplate liquid that the nanotube of Cu places step (2) to dispose, adopt the pulse electrodeposition method, the control depositing temperature is 40 ℃, and depositing time is 4h, the deposition cycle parameter is 45mA, 10ms,-45mA, 1ms, 0mA, 1s are with the SnO of doping Sb
2Deposit in the nanotube, prepare oxygen evolution potential high catalytic activity SnO
2-Sb
2O
5/ TiO
2-NTs electrode is product.
The above-mentioned description to embodiment is can understand and apply the invention for the ease of those skilled in the art.The person skilled in the art obviously can easily make various modifications to these embodiment, and needn't pass through performing creative labour being applied in the General Principle of this explanation among other embodiment.Therefore, the invention is not restricted to the embodiment here, those skilled in the art should be within protection scope of the present invention for improvement and modification that the present invention makes according to announcement of the present invention.
Claims (4)
1. a preparation method who processes the oxygen evolution potential electrode of fluorine containing organic waste water is characterized in that, the method adopts the pulse electrodeposition method to prepare doping type SnO on the titanium matrix Nano tube array of titanium dioxide for preparing through anodizing
2-Sb
2O
5/ TiO
2-NTs electrode is product, specifically may further comprise the steps:
(1) the pure metal titanium plate surface is carried out sanding and polishing with abrasive paper for metallograph, containing the NH of 0.05～1.0wt%
4F, the Na of 1.6～2.0wt%
2SO
4And 10～50wt% molecular weight be in the solution of 400 polyoxyethylene glycol take this titanium sheet as working electrode, platinized platinum is to electrode, carries out electrochemical anodic oxidation and processes, and obtains orderly TiO at titanium-based surface
2Nanometer pipe array electrode TiO
2-NTs adopts temperature programming to heat-treat in tube furnace at the electrode for preparing;
(2) with SnCl
22H
2O, SbCl
3, oxyethyl group aminopropyl trisiloxane tensio-active agent and hydrochloric acid is mixed with electroplate liquid, SnCl in this electroplate liquid
2Concentration be 0.2～0.5mol/L, SbCl
3Concentration be 0.2～0.4mol/L, the concentration of hydrochloric acid is 2～3mol/L, the concentration of oxyethyl group aminopropyl trisiloxane tensio-active agent is 0.2～0.3g/L;
(3) TiO for preparing with step (1)
2-NTs is working electrode, and platinized platinum is to electrode, and saturated calomel electrode is reference electrode, at 1～2mol L
-1Ammonium chloride solution in, under 40 ℃ of conditions of temperature, under the current potential of-1.5V, reduce 3s, then adopt 1.5mol L
-1CuSO
4By the pulse electrodeposition method, the control temperature is 40 ℃ Cu is deposited to TiO as electrolytic solution
2The bottom of-NTs, depositing time are 5～10min, will deposit the TiO of Cu again
2The electroplate liquid that-NTs places step (2) to dispose adopts the pulse electrodeposition method, and the control depositing temperature is 40 ℃, and depositing time is 2～4h, with the SnO of doping Sb
2Deposit to TiO
2Among-the NTs, prepare oxygen evolution potential high catalytic activity SnO
2-Sb
2O
5/ TiO
2-NTs electrode is product.
2. a kind of preparation method who processes the oxygen evolution potential electrode of fluorine containing organic waste water according to claim 1, it is characterized in that, heat treated temperature programming speed is 1～5 ℃/min in the described step (1), and thermal treatment temp is 450～550 ℃, and heat treatment time is 3～5h.
3. a kind of preparation method who processes the oxygen evolution potential electrode of fluorine containing organic waste water according to claim 1 is characterized in that, in the described step (3) with CuSO
4The deposition cycle parameter of the pulse electrodeposition method that adopts during as electrolytic solution is-70mA, 10ms 70mA, 1ms, 0mA, 1s.
4. a kind of preparation method who processes the oxygen evolution potential electrode of fluorine containing organic waste water according to claim 1 is characterized in that, in the described step (3) with the SnO of doping Sb
2Deposit to TiO
2The deposition cycle parameter of the pulse electrodeposition method the among-NTs is 45mA, 10ms ,-45mA, 1ms, 0mA, 1s.
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| CN103599797A (en) * | 2013-11-26 | 2014-02-26 | 同济大学 | Method for preparing SnO2 PC/CdS QDs composite photocatalyst with high-stability visible-light catalytic activity |
| CN104528890B (en) * | 2014-12-19 | 2017-01-18 | 深圳大学 | Ti/SnO2 electrode as well as preparation method and application |
| CN105858815A (en) * | 2016-05-04 | 2016-08-17 | 同济大学 | Preparation method for NiCo2S4@NiCo2O4 nanoneedle composite catalytic electrode with core-shell structure |
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