CN102191513A - Preparation method of insoluble titanium-based catalytic electrode - Google Patents
Preparation method of insoluble titanium-based catalytic electrode Download PDFInfo
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- CN102191513A CN102191513A CN 201110109054 CN201110109054A CN102191513A CN 102191513 A CN102191513 A CN 102191513A CN 201110109054 CN201110109054 CN 201110109054 CN 201110109054 A CN201110109054 A CN 201110109054A CN 102191513 A CN102191513 A CN 102191513A
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Abstract
The invention, which belongs to the technology field of catalytic electrode, discloses a preparation method of insoluble titanium-based catalytic electrode. According to the method, an electrodeposition method is employed to prepare an insoluble electrode SnO2-CeO2/Ti. The preparation method of the insoluble titanium-based catalytic electrode comprises the following steps: preparing a tinning plating solution, wherein a molar ratio of SnCl4 to NaSo4 to H2So4 is 8 to 12 : 80 to 120 : 0.8 to 1.2, and preparing a plating solution of plating cerium, wherein a molar ratio of CeCl4 to NaSO4 to H2SO4 is 0.8 to 1.2 : 80 to 120 : 0.8 to 1.2; and controlling current density and electroplate time to prepare an insoluble titanium-based catalytic electrode, wherein when the surface of the electrode blackens, the processes of washing and air drying are carried out, and then isothermal oxidation is carried out in a muffle furnace, followed by cooling to room temperature. The preparation method provided in the invention has an advantage of good controllability and is suitable for continuous industrial production. The surface of the prepared electrode has no crack and oxygen evolution overpotential of the electrode is high. In addition, the prepared electrode has high catalytic activity and high electrocatalysis efficiency. During the application of the insoluble titanium-based catalytic electrode, no chemical reagent is needed, so that there is no secondary pollution.
Description
Technical field
The present invention relates to a kind of preparation method of insoluble titanium base catalysis electrode and the technology of dye wastewater treatment using thereof, prepared SnO
2-CeO
2/ Ti insoluble electrode is made anode, is negative electrode with the stainless steel, but the technology of catalytic oxidation dye wastewater treatment using belongs to the catalysis electrode technical field.
Background technology
In recent years, development and progress along with printing technology, make bio-refractory organism such as PVA slurry, artificial silk alkali thing (mainly being O-phthalic acids material), New-type adjuvant enter water body, the environment and the mankind are caused serious harm, and traditional treatment process is difficult to these organic matter removals.Because electrocatalysis organic waste water has efficiently, non-secondary pollution, characteristics such as simple, quick, over nearly 10 years, electrocatalysis obtains broad development and application in field of waste water treatment., in the electrocatalysis Waste Water Treatment, electrode is the core of electric catalysis reactor, thereby manufactures the center of gravity of the anode material of good combination property for this invention.Traditional electrode exists overpotential for oxygen evolution low, catalytic activity is low, shortcomings such as the easy dissolving of electrode surface coating, and good insoluble anode requires that higher overpotential for oxygen evolution and catalytic activity are arranged, and in waste water, have advantages of higher stability and erosion resistance, higher overpotential for oxygen evolution and catalytic activity electrode are in electrolytic process, side reaction is few, the current efficiency height, and consumed power is few, can effectively reduce cost for wastewater treatment, increase economic efficiency.
Application number is that 200610144146.9 Chinese invention patent discloses a kind of method that adopts the iridium tantalum stannum oxide coating titanium electrode electrolyzing organic waste water, though this electrode can be removed multiple organism, clearance is not high, and current density is excessive, current efficiency is low, the technology for preparing electrode complexity.Application number is that 03133317.6 to adopt titanium be that the insoluble electrode that matrix is coated with plumbic oxide or tindioxide is an anode, and electrolysis 30～120min handles the refinery water of low chemical oxygen demand (COD), and is respond well.Ti-supported lead dioxide electric insoluble electrode Pyrogentisinic Acid has degradation property preferably, but has coating dissolved problem, and lead is heavy metal, produces secondary pollution.Application number 201010218092.2 has prepared a kind of titanium electrode material of coated with nanometre rhodium iridium coatings, electrode has the advantages that conductive effect is good, overpotential is low, current efficiency is high, but complicated process of preparation, electrode need be through repeating heating, cooling, " be full of cracks " takes place in top coat easily, and in electrolytic process, the corrosion particle is by the crevice corrosion base material, electrode catalyst performance shakiness, electrode life is short.Application number 200910085589.5 adopts sand-blast that the titanium matrix is carried out pre-treatment, has prepared titanium base IrO
2-Ta
2O
5Electrode.The method of sandblasting effectively raises the life-span of electrode, but Ir and Ta are precious metal, cost an arm and a leg, and therefore prepares electrode cost height, is difficult to realize industrial applications in field of waste water treatment.
Summary of the invention
In order to overcome the shortcoming and defect of above-mentioned prior art, primary and foremost purpose of the present invention provides a kind of easy manufacture technology of new electrode materials, prepares a kind of catalytic activity height, current efficiency height, the insoluble titanium base catalysis electrode SnO that electrode life is long
2-CeO
2/ Ti, utilize the electro-catalytic oxidation technology dye wastewater treatment using, when promptly adopting electrodip process to prepare insoluble titanium base catalysis electrode electrolysis treatment waste water from dyestuff, consume energy low and need not to add the chemical reagent non-secondary pollution, improve simultaneously the waste water from dyestuff clearance, can satisfy industrial needs.
Purpose of the present invention is achieved through the following technical solutions:
The preparation method of a kind of insoluble titanium base catalysis electrode of the present invention is characterized in that, adopts electrodip process to prepare SnO
2-CeO
2/ Ti insoluble electrode comprises the steps:
(1) preparation tin, cerium oxide electroplate liquid
Take by weighing tin chloride, sulfuric acid, sodium sulfate and be dissolved in the deionized water SnCl
4: NaSO
4: H
2SO
4Mol ratio is 8～12: 80～120: 0.8～1.2 is mixed with zinc-plated electroplate liquid, and the concentration of tin chloride is 0.4～0.8mol/L; Take by weighing in Cerium II Chloride, the sodium sulfate adding sulphuric acid soln CeCl
4: NaSO
4: H
2SO
4Mol ratio is 0.8～1.2: 80～120: 0.8～1.2 is mixed with plating cerium electroplate liquid, and the concentration of Cerium II Chloride is 0.04～0.08mol/L.
(2) pre-treatment of titanium matrix
The titanium sheet NaOH solution alkali cleaning oil removing 5～10min of mass concentration 10～20%, put into mass concentration 10～20%HCl solution then and soak 1～5min, after the cleaning of titanium sheet, carry out acid with the oxalic acid solution of massfraction 10～20% and boil etching, the etching time of titanium sheet is 80～150min, and it is stand-by to put into dehydrated alcohol;
(3) electrode preparation
In plating cerium and tin plating solution, control current density and electroplating time prepare insoluble titanium base catalysis electrode.At 10～30mAcm
-2Under the electric current, be anode with stainless steel, the plating cerium time is 10～40s, and the zinc-plated time is 150～300s, when electrode surface turns black, washes gently with deionized water.After treating that nature dries, be put in the retort furnace, room temperature begins to heat up, and heat-up rate is 1 ℃/min, is heated to 500 ℃, constant temperature oxidation 80～120min, and postcooling is to room temperature.
Adopt the electrode pair waste water from dyestuff of the high catalytic oxidation performance of the present invention's preparation to carry out electrocatalysis oxidation reaction, with the SnO of above-mentioned preparation
2-CeO
2/ Ti insoluble electrode is an anode, and stainless steel is a negative electrode, and waste water from dyestuff is carried out electrocatalysis oxidation reaction.Adopt double cathode, single anode electrode group, electrolytic condition: voltage 3～5V, pH value 3～7, interelectrode distance 5～25mm, electrolysis time 5～30min.Behind the catalytic oxidation azogeramine 4 waste water 30min, the COD clearance reaches 98.3%, and behind the catalytic oxidation 5min, the COD clearance reaches 97.5%, and the COD value is all reduced to below the 50mg/L, reaches discharging standards.
The present invention compares with relevant art, has following advantage:
(1) the present invention adopts electrodip process to prepare electrode to compare with squeegee process and need not to brush repeatedly, and preparation technology is simple, and controllability is good, is fit to industrial continuous production, and the electrode surface of preparation does not have " be full of cracks ", as shown in Figure 1.
(2) electrode that adopts the present invention to effect a permanent cure is carrying out need not to add chemical reagent in the electrolytic reaction process to waste water from dyestuff, non-secondary pollution, produce particle with strong oxidizing property such as hydroxyl radical free radical etc. in the electrolytic reaction process of the present invention, can be adsorbed on organism in electrode surface and the waste water does not have the direct reaction of selection, is carbonic acid gas and water with its mineralising.
(3) the electrode solidity to corrosion of the present invention's preparation is strong, and long service life through test, adopts the SnO of electrodip process preparation
2-CeO
2/ Ti insoluble electrode reaches 3.5～4 years work-ing life.
(4) the electrode overpotential for oxygen evolution height of the present invention's preparation, catalytic activity is strong, and electrocatalysis efficient height is through the prepared SnO of experiment test
2-CeO
2The overpotential for oxygen evolution of/Ti insoluble electrode reaches about 2.2V.Behind electrolysis rhodamine B waste water from dyestuff (COD is 150mg/L) 5min, COD clearance 97.5%, the power consumption of ton water is 0.02 degree.
(5) electrolytic reaction just can be carried out at normal temperatures, the reaction conditions gentleness, and electrolyzer is simple, takes up an area of to lack, but the mechanization degree height.
Description of drawings
Fig. 1 is the SEM figure of embodiment 1 electrode;
Fig. 2 is the XRD spectra of embodiment 1 electrode;
The catalytic electrolysis figure of the azogeramine 4 of Fig. 3 embodiment 1.
Embodiment
Embodiment 1
A kind of preparation of insoluble titanium base catalysis electrode and the method for dye wastewater treatment using thereof comprise the steps:
(1) preparation SnO
2-CeO
2/ Ti insoluble electrode
1. electroplate liquid preparation: be dissolved in the deionized water with a certain amount of tin chloride, sulfuric acid, sodium sulfate, be mixed with zinc-plated electroplate liquid, SnCl
4: NaSO
4: H
2SO
4Be 10: 100: 1 (mol ratio), the concentration of tin chloride is 0.5mol/L; Take by weighing a certain amount of Cerium II Chloride, sodium sulfate adds in the certain density dilute sulphuric acid, add a spot of Trisodium Citrate again and be mixed with plating cerium electroplate liquid CeCl
4: NaSO
4: H
2SO
4Be 1: 100: 1 (mol ratio), the concentration of Cerium II Chloride is 0.05mol/L.
2. titanium base material pre-treatment: it is 50mm * 25mm that base material is cut into process, removes the greasy dirt 10min of substrate surface with the 10NaOH alkali cleaning, and the base material after the oil removing is put into 10%HCl solution and soaked 5min.Taking-up is used deionized water rinsing after being heated to boiling etching 2h with 10% oxalic acid solution, and the dehydrated alcohol wiping is stand-by.
3. electrode preparation: at 20mAcm
-2Under the electric current, be anode with stainless steel, the plating cerium time is 20s, and the zinc-plated time is 180s, when electrode surface turns black, washes gently with deionized water.After treating that nature dries, be put in the retort furnace, room temperature begins to heat up, and heat-up rate is 1 ℃/min, is heated to 500 ℃, and constant temperature oxidation 120min, postcooling promptly make SnO to room temperature
2-CeO
2/ Ti insoluble electrode, the SEM figure and the XRD spectra of prepared electrode are seen Fig. 1 and Fig. 2.
(2) waste water from dyestuff is carried out electrolytic reaction
With the above-mentioned insoluble titanium base catalysis electrode for preparing is anode, stainless steel is a negative electrode, electrolyzer JJ-1 magnetic stirrer, adopt single anode, the double cathode group, the useful area of yin, yang electrode is 50mm * 25mm, and interelectrode distance is 10mm, uses 0.01mol/LNaOH and 0.01mol/LH respectively
2SO
4Regulate the pH value, need not to add chemical reagent in the electrolytic reaction process.At voltage is 4V, and the pH value is under 3 conditions, electrolysis 30min, and red 14 o'clock of electrolytic acid, the clearance of azogeramine 4 is up to 98.3%, and its electrolytic curve is seen Fig. 3; During the electrolysis rhodamine B, be 4V at voltage, the pH value is under 3 conditions, and behind the electrolysis 5min, the clearance of rhodamine B is up to 97.5%.
Embodiment 2
A kind of preparation of insoluble titanium base catalysis electrode and the method for dye wastewater treatment using thereof comprise the steps:
(1) preparation SnO
2-CeO
2/ Ti insoluble electrode
1. electroplate liquid preparation: be dissolved in the deionized water with a certain amount of tin chloride, sulfuric acid, sodium sulfate, be mixed with zinc-plated electroplate liquid, SnCl
4: NaSO
4: H
2SO
4Be 8: 80: 0.8 (mol ratio), the concentration of tin chloride is 0.4mol/L; Take by weighing a certain amount of Cerium II Chloride, sodium sulfate adds in the certain density dilute sulphuric acid, add a spot of Trisodium Citrate again and be mixed with plating cerium electroplate liquid CeCl
4: NaSO
4: H
2SO
4Be 0.8: 80: 0.8 (mol ratio), the concentration of Cerium II Chloride is 0.04mol/L.
2. titanium base material pre-treatment: identical with embodiment 1.
3. electrode preparation: at 10mAcm
-2Under the electric current, be anode with stainless steel, the plating cerium time is 20s, and the zinc-plated time is 150s, when electrode surface turns black, washes gently with deionized water.After treating that nature dries, be put in the retort furnace, room temperature begins to heat up, and heat-up rate is 1 ℃/min, is heated to 450 ℃, and constant temperature oxidation 120min, postcooling promptly make SnO to room temperature
2-CeO
2/ Ti insoluble electrode.
(2) waste water from dyestuff is carried out electrolytic reaction
With the insoluble titanium base catalysis electrode for preparing is anode, and stainless steel is a negative electrode, electrolyzer JJ-1 magnetic stirrer, adopt single anode, the double cathode group, the useful area of yin, yang electrode is 50mm * 25mm, interelectrode distance is 10mm, uses 0.01mol/LNaOH and 0.01mol/LH respectively
2SO
4Regulate the pH value, need not to add chemical reagent in the electrolytic reaction process.At voltage is 4V, and the pH value is under 3 conditions, red 14 o'clock of electrolytic acid, and behind the electrolysis 30min, the clearance of azogeramine 4 is up to 93.2%; At voltage is 4V, and the pH value is under 3 conditions, and during the electrolysis rhodamine B, behind the electrolysis 5min, the clearance of rhodamine B is up to 92.8%.
Embodiment 3
A kind of preparation of insoluble titanium base catalysis electrode and the method for dye wastewater treatment using thereof comprise the steps:
(1) preparation SnO
2-CeO
2/ Ti insoluble electrode
1. electroplate liquid preparation: be dissolved in the deionized water with a certain amount of tin chloride, sulfuric acid, sodium sulfate, be mixed with zinc-plated electroplate liquid, SnCl
4: NaSO
4: H
2SO
4Be 12: 120: 1.2 (mol ratio), the concentration of tin chloride is 0.8mol/L; Take by weighing a certain amount of Cerium II Chloride, sodium sulfate adds in the certain density dilute sulphuric acid, add a spot of Trisodium Citrate again and be mixed with plating cerium electroplate liquid CeCl
4: NaSO
4: H
2SO
4Be 1.2: 120: 1.2 (mol ratio), the concentration of Cerium II Chloride is 0.08mol/L.
2. titanium base material pre-treatment: identical with embodiment 1.
3. electrode preparation: at 30mAcm
-2Under the electric current, be anode with stainless steel, the plating cerium time is 30s, and the zinc-plated time is 300s, when electrode surface turns black, washes gently with deionized water.After treating that nature dries, be put in the retort furnace, room temperature begins to heat up, and heat-up rate is 1 ℃/min, is heated to 550 ℃, and constant temperature oxidation 120min, postcooling promptly make SnO to room temperature
2-CeO
2/ Ti insoluble electrode.
(2) waste water from dyestuff is carried out electrolytic reaction
With the insoluble titanium base catalysis electrode for preparing is anode, and stainless steel is a negative electrode, electrolyzer JJ-1 magnetic stirrer, adopt single anode, the double cathode group, the useful area of yin, yang electrode is 50mm * 25mm, interelectrode distance is 10mm, uses 0.01mol/LNaOH and 0.01mol/LH respectively
2SO
4Regulate the pH value, need not to add chemical reagent in the electrolytic reaction process.At voltage is 4V, and the pH value is under 3 conditions, red 14 o'clock of electrolytic acid, and behind the electrolysis 30min, the clearance of azogeramine 4 is up to 90.2%; At voltage is 4V, and the pH value is under 3 conditions, and during the electrolysis rhodamine B, behind the electrolysis 5min, the clearance of rhodamine B is up to 87.1%.
Claims (1)
1. the preparation method of an insoluble titanium base catalysis electrode is characterized in that, comprises the steps:
(1) preparation tin cerium oxide electroplate liquid
Take by weighing tin chloride, sulfuric acid, sodium sulfate and be dissolved in the deionized water SnCl
4: NaSO
4: H
2SO
4Mol ratio is 8～12: 80～120: 0.8～1.2 is mixed with zinc-plated electroplate liquid, and the concentration of tin chloride is 0.4～0.8mol/L; Take by weighing in Cerium II Chloride, the sodium sulfate adding sulphuric acid soln CeCl
4: NaSO
4: H
2SO
4Mol ratio is 0.8～1.2: 80～120: 0.8～1.2 is mixed with plating cerium electroplate liquid, and the concentration of Cerium II Chloride is 0.04～0.08mol/L;
(2) pre-treatment of titanium matrix
The titanium sheet NaOH solution alkali cleaning oil removing 5～10min of mass concentration 10～20%, put into mass concentration 10～20%HCl solution then and soak 1～5min, after the cleaning of titanium sheet, carry out acid with the oxalic acid solution of massfraction 10～20% and boil etching, the etching time of titanium sheet is 80～150min, and it is stand-by to put into dehydrated alcohol;
(3) electrode preparation
In step (1) plating cerium and tin plating solution, control current density and electroplating time prepare insoluble titanium base catalysis electrode, all at 10～30mAcm
-2Under the electric current, be anode with stainless steel, wherein plating the cerium time is 10～40s, the zinc-plated time is 150～300s, when electrode surface turns black, use deionized water rinsing, treat that nature dries after, be put in the retort furnace, room temperature begins to heat up, and heat-up rate is 1 ℃/min, is heated to 500 ℃, constant temperature oxidation 80～120min, postcooling is to room temperature.
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Cited By (8)
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| CN102560529A (en) * | 2012-03-05 | 2012-07-11 | 广州华秦机械设备有限公司 | Method for manufacturing cathode plate of water electrolysis device |
| CN102605386A (en) * | 2012-02-29 | 2012-07-25 | 华侨大学 | Method for preparing Ni/NiCo2O4 porous composite electrode for alkaline medium oxygen evolution |
| CN102838191A (en) * | 2012-09-27 | 2012-12-26 | 昆明理工大学 | Method for preparing composite anode material |
| CN105420774A (en) * | 2015-11-03 | 2016-03-23 | 中国第一汽车股份有限公司 | Method for preparing nano cerium oxide coating on metal carrier |
| CN105441999A (en) * | 2015-11-03 | 2016-03-30 | 中国第一汽车股份有限公司 | Method for preparing nanometer lanthanum oxide coating on metal carrier |
| CN105688677A (en) * | 2016-04-01 | 2016-06-22 | 中国科学院过程工程研究所 | Composite electrode for electrodialysis as well as preparation method and application thereof |
| CN108298645A (en) * | 2018-03-08 | 2018-07-20 | 南京工程学院 | Coated electrode and preparation method thereof suitable for desulfurization wastewater processing |
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Cited By (9)
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| CN102605386A (en) * | 2012-02-29 | 2012-07-25 | 华侨大学 | Method for preparing Ni/NiCo2O4 porous composite electrode for alkaline medium oxygen evolution |
| CN102560529A (en) * | 2012-03-05 | 2012-07-11 | 广州华秦机械设备有限公司 | Method for manufacturing cathode plate of water electrolysis device |
| CN102560529B (en) * | 2012-03-05 | 2014-09-10 | 广州华秦机械设备有限公司 | Method for manufacturing cathode plate of water electrolysis device |
| CN102838191A (en) * | 2012-09-27 | 2012-12-26 | 昆明理工大学 | Method for preparing composite anode material |
| CN105420774A (en) * | 2015-11-03 | 2016-03-23 | 中国第一汽车股份有限公司 | Method for preparing nano cerium oxide coating on metal carrier |
| CN105441999A (en) * | 2015-11-03 | 2016-03-30 | 中国第一汽车股份有限公司 | Method for preparing nanometer lanthanum oxide coating on metal carrier |
| CN105688677A (en) * | 2016-04-01 | 2016-06-22 | 中国科学院过程工程研究所 | Composite electrode for electrodialysis as well as preparation method and application thereof |
| CN108298645A (en) * | 2018-03-08 | 2018-07-20 | 南京工程学院 | Coated electrode and preparation method thereof suitable for desulfurization wastewater processing |
| CN111018222A (en) * | 2019-12-25 | 2020-04-17 | 四川阳森石油技术有限公司 | Natural bubble gas production wastewater treatment process |
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