CN103395864A - Method for modifying lead dioxide porous electrode by high pressure molding method - Google Patents
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Abstract
The invention discloses a method for modifying a lead dioxide porous electrode by a high pressure molding method. The method comprises the following steps of: mixing beta-PbO2 powder, lanthanum powder, activated carbon powder as well as organic bonding agents uniformly, air drying, putting into a mold, and finally carrying out high pressure molding to obtain a modified beta-PbO2 porous electrode, wherein the mass percentages of all the raw materials are as follows: 60-75% of beta-PbO2 powder, 10-25% of lanthanum powder and activated carbon powder and 15% of organic bonding agents. Compared with the traditional electrodeposition method, the method provided by the invention is simple to operate, has high practicality, can radically prevent the problem that the electrodeposition layer easily falls off. Compared with a beta-PbO2 electrode, the modified beta-PbO2 porous electrode prepared by the invention has the advantage that the catalytic performance is improved obviously.
Description
One, technical field
The present invention relates to a kind of preparation method of lead dioxide porous electrode, specifically a kind of method of high-pressure molding method modification lead dioxide porous electrode.
Two, background technology
Lead dioxide electrode has good corrosion resistance, electroconductibility is strong, overpotential for oxygen evolution is high, catalytic is good, low cost and other advantages, is well behaved anode material.
The preparation method of ti-supported lead dioxide electric pole all adopts the electrodip process preparation at present, be metallic titanium plate after pretreatment, put into electric depositing solution, choose other metal sheets of same homalographic and make negative electrode, control current density, temperature, concentration of electrolyte, electrodeposition time, to obtain the PbO of different thickness
2Settled layer, thus make PbO
2/ Ti electrode.Deposited film has two kinds, α type and β type, β-PbO
2Electroconductibility, erosion resistance be better than α-PbO
2So, often adopt β-PbO
2Prepare oxidizing electrode.The problem that this technology for preparing electrode exists is: 1, before the titanium matrix, pretreatment process is complicated, tediously long, more difficult control, and also Disposal quality directly affects follow-up electroplating process; 2, due in electroplating process, coating unavoidably has some crystal boundary gaps, and the oxygen that produces during electrolysis can see through crystal boundary gap oxidation matrix, forms the titanium oxide of poorly conductive, and the passivation matrix, cause electrode performance to aggravate, and affects PbO
2The job stability of electrode and work-ing life.Therefore, prepare in the process of electrode and generally first plate PbO
2Middle layer is to suppress passivation, and this process has increased electrode fabrication cost and process complexity, is difficult to fundamentally solve the problem of passivation of matrix.PbO because coating comes off
2The main forms of corrosion of electrode.For head it off, present method adopts the method for high-pressure molding to prepare PbO
2Electrode, the method is compared with traditional electrodip process, and is not only simple to operate, practical, and fundamentally avoided the caducous problem of deposition layer.
Three, summary of the invention
The present invention aims to provide a kind of method of high-pressure molding method modification lead dioxide porous electrode, has fundamentally avoided the caducous problem of deposition layer, and is simple to operate, practical, and improved the electro catalytic activity of lead dioxide porous electrode.
The method of high-pressure molding method modification lead dioxide porous electrode of the present invention is characterized in that:
With β-PbO
2Powder, lanthanum powder, active carbon powder and organic binder bond mix, and in the mould of packing into after air-dry, obtain modification β-PbO after high-pressure molding
2Porous electrode;
Each raw material constitutes by mass percentage:
β-PbO
2Powder 60-75%,
Lanthanum powder and active carbon powder 10-25%,
The mass ratio of described lanthanum powder and described active carbon powder is 1:1.
Described organic binder bond is ptfe emulsion.
The mass concentration of described ptfe emulsion is 60%, and the mass fraction that in raw material, organic binder bond adds is the mass fraction in the ptfe emulsion solute.
Pressure-controlling during high-pressure molding is at 20MPa, dwell time 2min.
Each raw material forms and is preferably by mass percentage:
β-PbO
2Powder 60-65%,
Lanthanum powder and active carbon powder 20-25%,
At PbO
2In add appropriate Rare Earth Lanthanum powder to have increased the specific surface area of electrode so that electrode surface is comparatively loose, not only accelerated the oxidizing reaction of electrode surface, and strengthened the absorption transformation of pollutent at electrode surface.Gac, owing to having good characterization of adsorption, can strengthen PbO
2The active site of electrode surface, can produce molecule or the ion of strong oxidation more in absorb polluted matter and solution, so efficient hardening the electrocatalytic oxidation property of electrode.
Compared with the prior art, beneficial effect of the present invention is embodied in:
1, the present invention adds appropriate lanthanum powder, has effectively increased the specific surface area of electrode, has not only accelerated the oxidizing reaction of electrode surface, and has strengthened the absorption transformation of pollutent at electrode surface;
2, the present invention adds proper amount of active carbon, has strengthened the active site of electrode surface, efficient hardening the electrocatalytic oxidation property of electrode;
3, the present invention adds appropriate ptfe emulsion, makes electrode surface that reunion occur, and forms hole, and this has improved the electrolytic efficiency of plumbic oxide to a certain extent.
4, the present invention compares with traditional electrodip process, and is not only simple to operate, practical, and fundamentally avoided the caducous problem of deposition layer.
Four, description of drawings
Fig. 1 is the β-PbO of the embodiment of the present invention 1 preparation
2XRD figure spectrum (A) and the standard diagram (B) thereof of powder.As can be seen from Figure 1, (25.379 ° of its 2 θ angles, 32.092 °, 36.262 °, 49.179 °, 52.129 °, 58.944 °, 60.876 °, 62.556 °, 66.889 °) fully corresponding with the diffractogram of the β type plumbic oxide of standard, only be embodied on the strength relationship of each angle and change to some extent.Therefore the made main crystalline phase of lead dioxide powder of present method is β-PbO
2, with α-PbO
2Compare β-PbO
2Have higher oxygen evolution potential and better conductivity, simultaneously β-PbO
2Spending rate in electrolytic process is than α-PbO
2Slow tens times.So β-PbO
2It is the electrode materials of excellent property.
Fig. 2 is pure β-PbO
2Electrode (A) and modification β-PbO of the present invention
2Porous electrode (being called for short modified electrode in figure) cyclic voltammetry curve (B).As can be seen from Figure 2, at pure β-PbO
2Electrode and modification β-PbO of the present invention
2The direct oxidation effect does not occur in these two kinds of electrode surfaces of porous electrode, the cyclic voltammetry curve of two kinds of electrodes does not all scan organic redox peak, electrochemical oxidation can not directly occur and be degraded gradually in this explanation methylene blue on electrode surface, its mechanism of degradation is because lead dioxide electrode has high deposition potential, thereby makes it can produce the more property strengthened intermediate material indirectly with dyestuff oxidative degradation in the electrocatalysis process.Simultaneously can find out modification β-PbO of the present invention
2The current value of porous electrode is apparently higher than pure PbO
2Electrode, this is to have higher electroconductibility and the cause of electrocatalysis because mixing of lanthanum powder and gac makes electrode.
Fig. 3 is pure β-PbO
2Electrode and modification β-PbO of the present invention
2The comparison diagram of porous electrode (being called for short modified electrode in figure) catalytic oxidation methylene blue.Wherein modified electrode adopts different lanthanum powder and gac mixed powder (abbreviation mixed powder) doping to compare.
Fig. 4 is pure β-PbO
2Electrode and modification β-PbO of the present invention
2The comparison diagram of porous electrode (being called for short modified electrode in figure) COD clearance.
Can find out from Fig. 3, Fig. 4, at PbO
2Mix a certain amount of mixed powder (lanthanum powder+gac, mass ratio are 1:1) in powder, made modification β-PbO
2The catalytic performance of porous electrode and pure β-PbO
2Electrode is compared and is significantly increased.
Five, embodiment
Embodiment 1: β-PbO
2The preparation of powder
The 10g lead acetate is dissolved in 20mL water, with NaOH, regulates pH value 9.0-10.0, to be dissolvedly add the 80mL clorox after complete, stir, react 6h under 90 ℃, after filtration, obtain dark-brown β-PbO after washing, drying
2Powder.
Embodiment 2: modification β-PbO
2The preparation of porous electrode
Take PbO by proportional quantity
2Powder, organic binder bond, lanthanum powder and gac mixed powder, the compression mold of packing into after mixing, keep 2min under the full-automatic pressing machine of 20MPa, obtain modification β-PbO
2Porous electrode.Described organic binder bond is the ptfe emulsion of mass concentration 60%.Each raw material addition formation by mass percentage sees the following form.
Embodiment 3: the experiment of electrode electro catalytic activity
At current density 25mA/cm
2, methylene blue (MB) starting point concentration 100mg/L, pH value of solution is 7.34, electrolyte solution Na
2SO
4Concentration 0.1mol/L, interelectrode distance is under the 1cm condition, investigates the impact of different lanthanum powder and gac mixed powder (abbreviation mixed powder) doping on MB percent of decolourization and COD clearance, the results are shown in Figure 3, Fig. 4.
Can find out from Fig. 3, Fig. 4, at PbO
2Mix a certain amount of mixed powder (lanthanum powder+gac, mass ratio are 1:1) in powder, made modification β-PbO
2The catalytic performance of porous electrode and pure β-PbO
2Electrode is compared and is significantly increased, and wherein the addition of mixed powder has better decolorizing effect when 20-25%.As can be seen from Figure 2, at pure β-PbO
2Electrode and modification β-PbO of the present invention
2The direct oxidation effect does not occur in these two kinds of electrode surfaces of porous electrode, the cyclic voltammetry curve of two kinds of electrodes does not all scan organic redox peak, electrochemical oxidation can not directly occur and be degraded gradually in this explanation methylene blue on electrode surface, its mechanism of degradation is because lead dioxide electrode has high deposition potential, thereby makes it can produce the more property strengthened intermediate material indirectly with dyestuff oxidative degradation in the electrocatalysis process.Simultaneously can find out modification β-PbO of the present invention
2The current value of porous electrode is apparently higher than pure PbO
2Electrode, this is to have higher electroconductibility and the cause of electrocatalysis because mixing of lanthanum powder and gac makes electrode.
Claims (6)
1. the method for a high-pressure molding method modification lead dioxide porous electrode is characterized in that:
With β-PbO
2Powder, lanthanum powder, active carbon powder and organic binder bond mix, and in the mould of packing into after air-dry, obtain modification β-PbO after high-pressure molding
2Porous electrode;
Each raw material constitutes by mass percentage:
β-PbO
2Powder 60-75%,
Lanthanum powder and active carbon powder 10-25%,
Organic binder bond 15%.
2. the method for high-pressure molding method modification lead dioxide porous electrode according to claim 1 is characterized in that:
The mass ratio of described lanthanum powder and described active carbon powder is 1:1.
3. the method for high-pressure molding method modification lead dioxide porous electrode according to claim 1 and 2 is characterized in that each raw material constitutes by mass percentage:
β-PbO
2Powder 60-65%,
Lanthanum powder and active carbon powder 20-25%,
Organic binder bond 15%.
4. the method for high-pressure molding method modification lead dioxide porous electrode according to claim 1 is characterized in that:
Described organic binder bond is ptfe emulsion.
5. the method for high-pressure molding method modification lead dioxide porous electrode according to claim 4 is characterized in that:
The mass concentration of described ptfe emulsion is 60%.
6. the method for high-pressure molding method modification lead dioxide porous electrode according to claim 1 is characterized in that:
Pressure-controlling during high-pressure molding is at 20MPa, dwell time 2min.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105000637A (en) * | 2015-06-24 | 2015-10-28 | 上海应用技术学院 | Cerium oxide-doped modified lead dioxide porous electrode and preparation method thereof |
| CN113233549A (en) * | 2021-04-30 | 2021-08-10 | 佛山经纬纳科环境科技有限公司 | Nano lead dioxide electrode and preparation method and application thereof |
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| JPH07278865A (en) * | 1994-04-05 | 1995-10-24 | Oriental Sangyo Kk | Carbonaceous electrode for generating carbon dioxide and its production |
| CN101020240A (en) * | 2007-03-16 | 2007-08-22 | 合肥工业大学 | Composite beta-PbO2/manganese ore powder electrode and prepn process of beta-PbO2 |
| CN101417831A (en) * | 2008-11-11 | 2009-04-29 | 北京师范大学 | Novel ti-supported lead dioxide electric pole and preparation method thereof |
| CN102677093A (en) * | 2012-05-30 | 2012-09-19 | 合肥工业大学 | Lead dioxide powder porous electrode and preparation method thereof |
-
2013
- 2013-07-25 CN CN2013103169604A patent/CN103395864A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH07278865A (en) * | 1994-04-05 | 1995-10-24 | Oriental Sangyo Kk | Carbonaceous electrode for generating carbon dioxide and its production |
| CN101020240A (en) * | 2007-03-16 | 2007-08-22 | 合肥工业大学 | Composite beta-PbO2/manganese ore powder electrode and prepn process of beta-PbO2 |
| CN101417831A (en) * | 2008-11-11 | 2009-04-29 | 北京师范大学 | Novel ti-supported lead dioxide electric pole and preparation method thereof |
| CN102677093A (en) * | 2012-05-30 | 2012-09-19 | 合肥工业大学 | Lead dioxide powder porous electrode and preparation method thereof |
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| 朱艳等: "二氧化铅粉末多孔电极处理氨氮废水的研究", 《环境工程技术学报》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105000637A (en) * | 2015-06-24 | 2015-10-28 | 上海应用技术学院 | Cerium oxide-doped modified lead dioxide porous electrode and preparation method thereof |
| CN113233549A (en) * | 2021-04-30 | 2021-08-10 | 佛山经纬纳科环境科技有限公司 | Nano lead dioxide electrode and preparation method and application thereof |
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Application publication date: 20131120 |