CN102531108A - Lead dioxide electrode, production method thereof, application of lead dioxide electrode to quickly decoloring azo dyes and method for quickly decoloring azo dyes by using lead dioxide electrode - Google Patents
Lead dioxide electrode, production method thereof, application of lead dioxide electrode to quickly decoloring azo dyes and method for quickly decoloring azo dyes by using lead dioxide electrode Download PDFInfo
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- YADSGOSSYOOKMP-UHFFFAOYSA-N dioxolead Chemical compound O=[Pb]=O YADSGOSSYOOKMP-UHFFFAOYSA-N 0.000 title claims abstract description 55
- 238000000034 method Methods 0.000 title claims abstract description 31
- 239000000987 azo dye Substances 0.000 title claims abstract description 15
- 238000004519 manufacturing process Methods 0.000 title abstract 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 70
- 239000010936 titanium Substances 0.000 claims abstract description 70
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 70
- 239000003513 alkali Substances 0.000 claims abstract description 22
- 238000001354 calcination Methods 0.000 claims abstract description 10
- 238000005498 polishing Methods 0.000 claims abstract description 10
- 238000005406 washing Methods 0.000 claims abstract description 5
- 238000004140 cleaning Methods 0.000 claims description 21
- 239000008151 electrolyte solution Substances 0.000 claims description 21
- 239000000243 solution Substances 0.000 claims description 21
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 18
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
- 238000005554 pickling Methods 0.000 claims description 15
- 239000000975 dye Substances 0.000 claims description 14
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 12
- 230000008569 process Effects 0.000 claims description 11
- 238000002360 preparation method Methods 0.000 claims description 10
- 239000002351 wastewater Substances 0.000 claims description 10
- 230000003197 catalytic effect Effects 0.000 claims description 8
- 238000012986 modification Methods 0.000 claims description 8
- 230000004048 modification Effects 0.000 claims description 7
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 6
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 6
- 239000010949 copper Substances 0.000 claims description 6
- 229910052802 copper Inorganic materials 0.000 claims description 6
- 238000005530 etching Methods 0.000 claims description 6
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 6
- 235000006408 oxalic acid Nutrition 0.000 claims description 6
- 230000003647 oxidation Effects 0.000 claims description 6
- 238000007254 oxidation reaction Methods 0.000 claims description 6
- -1 polyoxyethylene Polymers 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- 239000008367 deionised water Substances 0.000 claims description 3
- 229910021641 deionized water Inorganic materials 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 3
- 229910021642 ultra pure water Inorganic materials 0.000 claims description 3
- 239000012498 ultrapure water Substances 0.000 claims description 3
- GFLJTEHFZZNCTR-UHFFFAOYSA-N 3-prop-2-enoyloxypropyl prop-2-enoate Chemical compound C=CC(=O)OCCCOC(=O)C=C GFLJTEHFZZNCTR-UHFFFAOYSA-N 0.000 claims 2
- 229920000371 poly(diallyldimethylammonium chloride) polymer Polymers 0.000 claims 2
- 239000000126 substance Substances 0.000 abstract description 2
- 239000002253 acid Substances 0.000 abstract 1
- 239000007772 electrode material Substances 0.000 description 15
- 230000000694 effects Effects 0.000 description 8
- 244000137852 Petrea volubilis Species 0.000 description 3
- 229910010413 TiO 2 Inorganic materials 0.000 description 3
- 238000004042 decolorization Methods 0.000 description 3
- 239000004519 grease Substances 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 239000003643 water by type Substances 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000004737 colorimetric analysis Methods 0.000 description 2
- 238000002798 spectrophotometry method Methods 0.000 description 2
- 206010033799 Paralysis Diseases 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 238000009303 advanced oxidation process reaction Methods 0.000 description 1
- 150000004982 aromatic amines Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000003851 biochemical process Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000004061 bleaching Methods 0.000 description 1
- 230000000711 cancerogenic effect Effects 0.000 description 1
- 231100000315 carcinogenic Toxicity 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000005345 coagulation Methods 0.000 description 1
- 230000015271 coagulation Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 229910003460 diamond Inorganic materials 0.000 description 1
- 239000010432 diamond Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- IXSZQYVWNJNRAL-UHFFFAOYSA-N etoxazole Chemical compound CCOC1=CC(C(C)(C)C)=CC=C1C1N=C(C=2C(=CC=CC=2F)F)OC1 IXSZQYVWNJNRAL-UHFFFAOYSA-N 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- ZUHZZVMEUAUWHY-UHFFFAOYSA-N n,n-dimethylpropan-1-amine Chemical compound CCCN(C)C ZUHZZVMEUAUWHY-UHFFFAOYSA-N 0.000 description 1
- 239000010815 organic waste Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
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Abstract
The invention discloses a lead dioxide electrode, a production method thereof, an application of the lead dioxide electrode to quickly decoloring azo dyes and a method for quickly decoloring azo dyes by using the lead dioxide electrode, wherein the electrode is obtained after polishing, alkali washing, acid washing, electrolyzing and calcinating a titanium plate. Under the condition that the current is constant, the produced modified lead dioxide electrode is utilized to decolor the azo dyes through controlling current density, conduction time and other factors. The method does not bring other chemical substances in, and does not cause secondary pollution, and has the advantages of temperate reaction condition, convenience for operation and the like. After a power supply is connected, the azo dyes can be effectively decolored within a short time, the decoloring efficiency is high, and the speed is fast.
Description
Technical field
The invention belongs to the environmental pollution improvement field, relate to a kind of method of electrochemical catalytic oxidation, specifically be a kind of lead dioxide electrode, its preparation method and utilizing electrochemical catalytic oxidation to make the azoic dyestuff application in the decolouring fast.
Background technology
Waste water from dyestuff is the main source that textile industry water pollutes; Has " three high one is low " obvious characteristic; Be characteristics such as colourity is high, toxicity is high, salinity is high, BOD/COD is low; Thereby be difficult to by biological degradation, not only can't use traditional biochemical process that it is effectively removed, also might cause the paralysis of biochemical system.
Azo dyes is the staple commodities classification of dyestuff, in dyestuff, uses the most extensively, and nearly 2/3 is azo dyes in the dyestuff that on market, circulates.As one of which, contain one or more aromatic ring structures, azo dyes character is very stable, and very easily decomposes the generation carcinogenic aromatic amine under the anaerobic environment, is one of current waste water from dyestuff that pollutes very seriously, demands urgently administering of China.
The treatment technology of waste water from dyestuff mainly contains Coagulation Method, advanced oxidation processes, absorption method, membrane separation process and electrochemical process etc. at present.These method general technology long flow paths, treating processes is slow, and intermediate product is many, causes secondary pollution easily, and cost is also relatively more expensive.
In recent years, utilized electrochemical catalytic oxidation technical finesse organic waste water to become the domestic and international research focus.A lot of about the relevant report of utilizing electrode materials catalyzed oxidation phenolic wastewater at present; Also fewer about the application and the report of degraded azo class waste water, this mainly is owing to fail to develop the electrode materials that has effective catalytic effect for the complicated pollutent of this class formation of dyestuff.Therefore, many investigators are just attempting to prepare the electrode that baroque pollutent is also had extremely strong catalytic capability, wherein to boron-doped diamond, PbO
2Modification etc. classical electrode is present research focus.
Summary of the invention
Technical problem to be solved by this invention provides a kind of modification lead dioxide electrode and preparation method thereof, the application that this electrode can effectively decolour to azo dyes fast.
A kind of lead dioxide electrode material of the present invention, it is prepared from following steps:
1) the titanium plate is polished, make titanium plate surface demonstrate the light grey gloss of homogeneous;
2) the titanium plate after will polishing carries out alkali cleaning, removes the pollutent on titanium plate surface;
3) the titanium plate after the alkali cleaning carries out pickling, removes the TiO on titanium plate surface
2
4) the titanium plate after step 3) is handled is made anode, Pt is a negative electrode, with 0.5 ~ 2 wt%NaF, 1 ~ 5 wt%Na
2SO
4, 5 ~ 20 wt% polyoxyethylene glycol and ultrapure water be configured to electrolytic solution, the constant voltage etching is 1 ~ 3 hour under 15 ~ 25 V conditions, then in retort furnace in 500 ~ 550 ℃ of calcinings 1.5 ~ 3 hours down;
5) with Pt be anode, the titanium plate after step 4) is handled is made negative electrode, 0.5 ~ 1.5 mol/L (NH
4)
2SO
4Be electrolytic solution, the constant voltage energising is 0.1 ~ 10 minute under 1.5 ~ 2 V conditions;
6) titanium plate that will be after step 5) is handled is at 1 ~ 2 mol/L CuSO
4Under 35 ~ 45 ℃ of conditions, adopt pulse current method to handle in the solution 5 ~ 15 minutes;
7) with above-mentioned steps 6) titanium plate after handling is as anode, and copper coin is a negative electrode, and electrolytic solution is by 0.05 ~ 0.5 mol/L HNO
3, 0.1 ~ 1.5 mol/L Pb (NO
3)
2, 0.01 ~ 0.1 mol/L NaF and 0.1 ~ 1 wt% PDDA mix, at constant current 5 ~ 40 mA/cm
2, 50 ~ 90 ℃, handle after 30 ~ 90 minutes, use the deionized water thorough washing totally promptly to get the modification lead dioxide electrode.
Step 2) process of alkali cleaning is that the titanium plate after the polishing is immersed 40 ~ 60 wt% NaOH solution, and the pollutent on titanium plate surface is removed in 60 ~ 80 ℃ of following alkali cleanings 2 ~ 4 hours.
The process of step 3) pickling is that the titanium plate after the alkali cleaning immerses in 10 ~ 20 wt% oxalic acid solutions in 60 ~ 95 ℃ of following pickling 2 ~ 4 hours.
The process of step 6) pulse current method is: handle 5 ~ 15 ms with the cathode pulse of-50 ~-80 mA earlier, handle 0.5 ~ 2 ms with the anodic pulse of 60 ~ 80 mA again, then lax 0.5 ~ 5 s repeats above-mentioned steps then.
The present invention also provides the application of this lead dioxide electrode material in azo dyes decolours fast.
Lead dioxide electrode material of the present invention makes the azoic dyestuff method of decolouring fast in electrochemical catalytic oxidation, the steps include: that the modification plumbic oxide with preparation is an anode, constant current 50 ~ 500 mA/cm
2Under the condition, place phenolic wastewater, the quick decolouring of switching on and realizing azoic dyestuff in 0.5 ~ 5 hour.
Spacing is 10 millimeters between above-mentioned anode and cathode.
Modification plumbic oxide of the present invention is an anode, at traditional P bO
2Add tensio-active agent polydiene propyl-dimethyl amine hydrochlorate (PDDA) in the electrode synthetic electrolytic solution; Through the control hydrothermal synthesizing condition; To improve the homogeneity of electrode surface plumbic oxide size distribution, increase electrode specific surface area, it is active to improve electrode catalyst.Through controlled step 7) temperature can so that to mainly be the strong β-PbO of catalytic activity
2, improve the electrode catalyst performance
The present invention compared with prior art has the following advantages: the chromophoric group that (1) can be destroyed azo dyes fast, can decolour fast and effectively.(2) life-span of the electrode that uses longer, whole removal device is simple, easy to operate, has advantages such as the life-span is long, easy and simple to handle.(3) not additional other chemical substances of introducing have been avoided secondary pollution when reducing cost.(4) only need simple passing through control current density and conduction time, can realize effective decolouring azo dyes.
Description of drawings:
Fig. 1 is electrode materials of the present invention decolorizing effect to 50 mg/L Kn-B when the different electric flow density,
Fig. 2 is that electrode materials is at current density 150 mA/cm
2The time to the decolorizing effect of different starting point concentration Kn-B.
Embodiment:
Below in conjunction with embodiment the present invention is described further.
1, the preparation method of electrode materials
Embodiment 1:
1) successively the titanium plate is polished with thickness sand paper respectively, make titanium plate surface demonstrate the light grey gloss of homogeneous.
2) the titanium plate after will polishing immerses 40 wt% NaOH solution, and the pollutents such as grease on titanium plate surface are removed in 80 ℃ of following alkali cleanings 2 hours.
3) the titanium plate after the alkali cleaning immerses in the oxalic acid solution of 15 wt% in 90 ℃ of following pickling 2 hours, removes titanium plate surface TiO
2
4) make anode with the titanium plate after the pickling, the Pt electrode is a negative electrode, and electrolytic solution is by 0.8 wt%NaF, 1.6 wt%Na
2SO
4, 10 wt% polyoxyethylene glycol and 87.6 wt% ultrapure waters form, the constant voltage etching is 1 hour under 25 V conditions, then in retort furnace in 500 ℃ of calcinings 3 hours down.
5) be anode with the Pt electrode, the titanium plate after the calcining is made negative electrode, 1 mol/L (NH
4)
2SO
4Be electrolytic solution, the constant voltage energising is 20 seconds under 1.5 V conditions.
6) titanium plate that will be after step 5) is handled is at 1 mol/L CuSO
4Under 45 ℃ of conditions, adopt pulse current method in the solution: cathode pulse (70 mA, 10 ms), anodic pulse (70 mA, 1 ms), lax (0 mA, 1 s) handled 5 minutes.
7) with above-mentioned steps 6) titanium plate after handling is as anode, and copper coin is a negative electrode, with 0.05 mol/L HNO
3, 0.5 mol/L Pb (NO
3)
2, 0.04 mol/L NaF and 0.45 wt% PDDA mixing solutions be as electrolytic solution, at constant current 25 mA/cm
2, 80 ℃, handled 40 minutes.
Above-mentioned anode and cathode interelectrode distance is 10 millimeters.
Embodiment 2:
1) successively the titanium plate is polished with thickness sand paper respectively, make titanium plate surface demonstrate the light grey gloss of homogeneous.
2) the titanium plate after will polishing immerses 60 wt% NaOH solution, and the pollutents such as grease on titanium plate surface are removed in 60 ℃ of following alkali cleanings 4 hours.
3) the titanium plate after the alkali cleaning immerses in the oxalic acid solution of 10 wt% in 60 ℃ of following pickling 2 hours, removes titanium plate surface TiO
2
4) make anode with the titanium plate after the pickling, the Pt electrode is a negative electrode, and electrolytic solution is by 0.5wt%NaF, 1wt%Na
2SO
4, 5wt% polyoxyethylene glycol and 93.5 wt% ultrapure waters form, the constant voltage etching is 3 hours under the 15V condition, then in retort furnace in 550 ℃ of calcinings 1.5 hours down.
5) be anode with the Pt electrode, the titanium plate after the calcining is made negative electrode, 0.5 mol/L (NH
4)
2SO
4Be electrolytic solution, the constant voltage energising is 20 seconds under 1.5 V conditions.
6) titanium plate that will be after step 5) is handled is at 2 mol/L CuSO
4Under 35 ℃ of conditions, adopt pulse current method in the solution: cathode pulse (50 mA, 5 ms), anodic pulse (60 mA, 0.5 ms), lax (0 mA, 0.5 s) handled 15 minutes.
7) with above-mentioned steps 6) titanium plate after handling is as anode, and copper coin is a negative electrode, with 0. 05 mol/L HNO
3, 0.1mol/L Pb (NO
3)
2, 0.01mol/L NaF and 0.1wt% PDDA mixing solutions be as electrolytic solution, at constant current 5 mA/cm
2, 50 ℃, handled 90 minutes.
Above-mentioned anode and cathode interelectrode distance is 10 millimeters.
Embodiment 3:
1) successively the titanium plate is polished with thickness sand paper respectively, make titanium plate surface demonstrate the light grey gloss of homogeneous.
2) the titanium plate after will polishing immerses 50 wt% NaOH solution, and the pollutents such as grease on titanium plate surface are removed in 70 ℃ of following alkali cleanings 3 hours.
3) the titanium plate after the alkali cleaning immerses in the oxalic acid solution of 20 wt% in 95 ℃ of following pickling 4 hours, removes titanium plate surface TiO
2
4) make anode with the titanium plate after the pickling, the Pt electrode is a negative electrode, and electrolytic solution is by 2 wt%NaF, 5 wt%Na
2SO
4, 20 wt% polyoxyethylene glycol and 73 wt% ultrapure waters form, the constant voltage etching is 2 hours under 25 V conditions, then in retort furnace in 550 ℃ of calcinings 3 hours down.
5) be anode with the Pt electrode, the titanium plate after the calcining is made negative electrode, 1.5 mol/L (NH
4)
2SO
4Be electrolytic solution, the constant voltage energising is 10 minutes under the 2V condition.
6) titanium plate that will be after step 5) is handled is at 2 mol/L CuSO
4Under 45 ℃ of conditions, adopt pulse current method in the solution: cathode pulse (80 mA, 15 ms), anodic pulse (80 mA, 2 ms), lax (0 mA, 5 s) handled 30 minutes.
7) with above-mentioned steps 6) titanium plate after handling is as anode, and copper coin is a negative electrode, with 0.5 mol/L HNO
3, 1.5 mol/L Pb (NO
3)
2, 0.1 mol/L NaF and 1 wt% PDDA mixing solutions be as electrolytic solution, at constant current 40mA/cm
2, 90 ℃, handled 90 minutes.
Above-mentioned anode and cathode interelectrode distance is 10 millimeters.
2, the present invention is an instance with azo dyes HFGR REACTIVE Black HFGR Kn-B also, and the decolorizing effect of this electrode materials to Kn-B waste water is provided.
Embodiment 1:
A) with prepared electrode materials as anode, the Pt electrode is a negative electrode, and 100 mL are contained 50 mg/L HFGR REACTIVE Black HFGRs, 0.25 mol/L Na
2SO
4Simulated wastewater as electrolytic solution, constant current 150 mA/cm under the room temperature
2
B) according to step a), 10 min that switch on respectively, 20 min, 30 min, 40 min, 50 min, 1 h, 1.5 h, 2 h, 3 h.
C) sample of above-mentioned different conduction times is done the colourity analysis respectively, what wherein colorimetric analysis was adopted is spectrophotometry.
D) calculate decolorizing effect, wherein percent of decolourization/%=100% (A
0-A
e)/A
0
Embodiment 2:
A) with prepared electrode materials as anode, the Pt electrode is a negative electrode, and 100 mL are contained 100 mg/L HFGR REACTIVE Black HFGRs, 0.25 mol/L Na
2SO
4Simulated wastewater as electrolytic solution, constant current 150 mA/cm under the room temperature
2
B) according to step a), 10 min that switch on respectively, 20 min, 30 min, 40 min, 50 min, 1 h, 1.5 h, 2 h, 3 h.
C) sample of above-mentioned different conduction times is done the colourity analysis respectively, what wherein colorimetric analysis was adopted is spectrophotometry.
D) calculate decolorizing effect, wherein percent of decolourization/%=100% (A
0-A
e)/A
0
Fig. 1 is electrode materials of the present invention decolorizing effect to 50 mg/L Kn-B when the different electric flow density, and Fig. 2 is that electrode materials is at current density 150 mA/cm
2The time to the decolorizing effect of different starting point concentration Kn-B.By scheming visible current density at 50 ~ 200 mA/cm
2Between the time, all can realize that current density is big more to the quick decolouring of 50 mg/L Kn-B, decolorization rate is fast more; Along with the increase of current density, it is more and more littler for the promoter action of decolorizing effect to increase current density.When current density is 150 mA/cm
2The time, this electrode materials all can be realized decolouring fast to the Kn-B of starting point concentration 50 ~ 150 mg/L, and starting point concentration is big more, and required bleaching time is long more.In sum, this electrode materials can realized decolouring fast and effectively to the Kn-B dyestuff in the finite concentration scope in the current density range more widely.
More than be thinking of the present invention and implementation method, should be pointed out that for those skilled in the art, under the prerequisite that does not break away from the principle of the invention, can also make some improvement, these improvement also should be regarded as protection scope of the present invention.
Claims (10)
1. lead dioxide electrode is characterized in that being prepared from following steps:
1) the titanium plate is polished, make titanium plate surface demonstrate the light grey gloss of homogeneous;
2) the titanium plate after will polishing carries out alkali cleaning, removes the pollutent on titanium plate surface;
3) the titanium plate after the alkali cleaning carries out pickling, removes the TiO on titanium plate surface
2
4) the titanium plate after step 3) is handled is made anode, Pt is a negative electrode, with 0.5 ~ 2 wt%NaF, 1 ~ 5 wt%Na
2SO
4, 5 ~ 20 wt% polyoxyethylene glycol and ultrapure water be configured to electrolytic solution, the constant voltage etching is 1 ~ 3 hour under 15 ~ 25 V conditions, then in retort furnace in 500 ~ 550 ℃ of calcinings 1.5 ~ 3 hours down;
5) with Pt be anode, the titanium plate after step 4) is handled is made negative electrode, 0.5 ~ 1.5 mol/L (NH
4)
2SO
4Be electrolytic solution, the constant voltage energising is 0.1 ~ 10 minute under 1.5 ~ 2 V conditions;
6) titanium plate that will be after step 5) is handled is at 1 ~ 2 mol/L CuSO
4Under 35 ~ 45 ℃ of conditions, adopt pulse current method to handle in the solution 5 ~ 30 minutes;
7) with above-mentioned steps 6) titanium plate after handling is as anode, and copper coin is a negative electrode, and electrolytic solution is by 0.05 ~ 0.5 mol/L HNO
3, 0.5 ~ 1.5 mol/L Pb (NO
3)
2, 0.01 ~ 0.1 mol/L NaF and 0.1 ~ 1 wt% PDDA mix, at constant current 5 ~ 40 mA/cm
2, 50 ~ 90 ℃, handle after 30 ~ 90 minutes, use the deionized water thorough washing totally promptly to get the modification lead dioxide electrode.
2. lead dioxide electrode according to claim 1 is characterized in that step 2) process of alkali cleaning is that the titanium plate after the polishing is immersed 40 ~ 60 wt% NaOH solution, the pollutent on titanium plate surface is removed in 60 ~ 80 ℃ of following alkali cleanings 2 ~ 4 hours.
3. lead dioxide electrode according to claim 1 and 2, the process that it is characterized in that the step 3) pickling are that the titanium plate after the alkali cleaning immerses in 10 ~ 20 wt% oxalic acid solutions in 60 ~ 95 ℃ of following pickling 2 ~ 4 hours.
4. lead dioxide electrode according to claim 1 and 2; The process that it is characterized in that the step 6) pulse current method is: handle 5 ~ 15 ms with the cathode pulse of-50 ~-80 mA earlier; Handle 0.5 ~ 2 ms with the anodic pulse of 60 ~ 80 mA again, then lax 0.5 ~ 5 s repeats above-mentioned steps then.
5. the preparation method of a lead dioxide electrode is characterized in that may further comprise the steps:
1) the titanium plate is polished, make titanium plate surface demonstrate the light grey gloss of homogeneous;
2) the titanium plate after will polishing carries out alkali cleaning, removes the pollutent on titanium plate surface;
3) the titanium plate after the alkali cleaning carries out pickling, removes the TiO on titanium plate surface
2
4) the titanium plate after step 3) is handled is made anode, Pt is a negative electrode, with 0.5 ~ 2wt%NaF, 1 ~ 5 wt%Na
2SO
4, 5 ~ 20 wt% polyoxyethylene glycol and ultrapure water be configured to electrolytic solution, the constant voltage etching is 1 ~ 3 hour under 15 ~ 25 V conditions, then in retort furnace in 500 ~ 550 ℃ of calcinings 1.5 ~ 3 hours down;
5) with Pt be anode, the titanium plate after step 4) is handled is made negative electrode, 0.5 ~ 1.5 mol/L (NH
4)
2SO
4Be electrolytic solution, the constant voltage energising is 0.1 ~ 10 minute under 1.5 ~ 2 V conditions;
6) titanium plate that will be after step 5) is handled is at 1 ~ 2 mol/L CuSO
4Under 35 ~ 45 ℃ of conditions, adopt pulse current method to handle in the solution 5 ~ 15 minutes;
7) with above-mentioned steps 6) titanium plate after handling is as anode, and copper coin is a negative electrode, and electrolytic solution is by 0.05 ~ 0.5 mol/L HNO
3, 0.1 ~ 1.5 mol/L Pb (NO
3)
2, 0.01 ~ 0.1 mol/L NaF and 0.1 ~ 1 wt% PDDA mix, at constant current 5 ~ 40 mA/cm
2, 50 ~ 90 ℃, handle after 30 ~ 90 minutes, use the deionized water thorough washing totally promptly to get the modification lead dioxide electrode.
6. the preparation method of lead dioxide electrode according to claim 5 is characterized in that step 2) process of alkali cleaning is that the titanium plate after the polishing is immersed 40 ~ 60 wt% NaOH solution, the pollutent on titanium plate surface is removed in 60 ~ 80 ℃ of following alkali cleanings 2 ~ 4 hours.
7. according to the preparation method of claim 5 or 6 described lead dioxide electrodes, the process that it is characterized in that the step 3) pickling is that the titanium plate after the alkali cleaning immerses in 10 ~ 20 wt% oxalic acid solutions in 60 ~ 95 ℃ of following pickling 2 ~ 4 hours.
8. according to the preparation method of claim 5 or 6 described lead dioxide electrodes; The process that it is characterized in that the step 6) pulse current method is: handle 5 ~ 15 ms with the cathode pulse of-50 ~-80 mA earlier; Handle 0.5 ~ 2 ms with the anodic pulse of 60 ~ 80 mA again; Then lax 0.5 ~ 5 s repeats above-mentioned steps then.
9. the application of the described lead dioxide electrode of claim 1 in azo dyes decolours fast.
10. a lead dioxide electrode makes the azoic dyestuff method of decolouring fast in electrochemical catalytic oxidation, and it is characterized in that step is: the modification plumbic oxide with preparation is an anode, constant current 50 ~ 500 mA/cm
2Under the condition, place phenolic wastewater, the quick decolouring of switching on and realizing azoic dyestuff in 0.5 ~ 5 hour.
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|---|---|---|---|
| CN2012100065149A CN102531108A (en) | 2012-01-11 | 2012-01-11 | Lead dioxide electrode, production method thereof, application of lead dioxide electrode to quickly decoloring azo dyes and method for quickly decoloring azo dyes by using lead dioxide electrode |
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|---|---|---|---|
| CN2012100065149A CN102531108A (en) | 2012-01-11 | 2012-01-11 | Lead dioxide electrode, production method thereof, application of lead dioxide electrode to quickly decoloring azo dyes and method for quickly decoloring azo dyes by using lead dioxide electrode |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
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