CN101445281A - Laccase-modified electrode and method for removing chlorophenol pollutants from water by utilizing same - Google Patents
Laccase-modified electrode and method for removing chlorophenol pollutants from water by utilizing same Download PDFInfo
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- CN101445281A CN101445281A CNA2009100002010A CN200910000201A CN101445281A CN 101445281 A CN101445281 A CN 101445281A CN A2009100002010 A CNA2009100002010 A CN A2009100002010A CN 200910000201 A CN200910000201 A CN 200910000201A CN 101445281 A CN101445281 A CN 101445281A
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Abstract
The invention relates to a laccase-modified electrode and a method for removing chlorophenol pollutants from water by utilizing same, which belong to the application field of water treatment technology. The electrode capable of oxidizing chlorophenol pollutants in water is produced by selecting a Ti-based material as a carrier, subjecting the Ti-based material to acid-etching, plating an Sn-Sb oxide bottom coating by the thermal decomposition method, electroplating an alpha-PbO2 intermediate layer by employing alkaline solutions, forming a beta-PbO2-containing surface layer doped with a reactive metal (such as Bi, Ni, La, Ce or Er) by employing acidic composite electroplating baths, and modifying the electrode surface with chitosan-immobilized laccase by employing film-forming liquids. By applying a certain amount of an external voltage to the laccase-modified electrode as the anode and the stainless steel material as the cathode, the chlorophenol pollutants in water are removed with high efficiency. The laccase-modified electrode with the advantages of easy operation and convenient management is suitable for small-scale and decentralized waste water treatments and feed water treatments.
Description
Technical field
The present invention relates to a kind of laccase modified electrode and use this electrode to remove the method for chlorophenol pollutants in the water, specifically be that a kind of chitosan-immobilized laccase is modified the ti-supported lead dioxide electric pole that contains a kind of reactive metal (as bismuth, nickel, lanthanum, cerium or erbium) and fluorine, under the situation of energising,, belong to the Application Areas of water technology with the chlorophenol oxidation in the water.
Background technology
Chlorophenol pollutant has higher toxicity and stronger stability, enter water body on a small quantity and just can produce serious publilc health risk, therefore, this class material has been subjected to the extensive concern of countries in the world to the pollution of water surrounding, and the efficient novel method of removing chlorophenol pollutant in the water of research has become a focus in the present water treatment field.
Electrochemical oxidation can directly or indirectly produce OH by the electrode reaction that catalytic activity is arranged at normal temperatures and pressures as a kind of advanced oxidization method, thus most organic pollutant in effective degradation water.The key factor of decision electrochemical oxidation usefulness is the preparation of high-efficient electrode.PbO
2Satisfactory electrical conductivity with metalloid, titanium base PbO
2Electrode because in the aqueous solution, have the oxygen evolution potential height, oxidation capacity is strong, solidity to corrosion good, good conductivity, can be subjected to attracting attention of numerous investigators in recent years by characteristics such as big electric currents.Present a lot of research is devoted to PbO
2Electrode surface carries out chemically modified, to improve the original character of electrode, realizes the functional design of electrode.In electrochemical oxidation process, the transition process of pollutent in electric field makes optionally bonding and the enrichment in the anodic decorative layer of electronegative organic matter, thereby improves oxidative degradation usefulness.
Laccase is a kind of cupric polyphenoloxidase, the different substrate of the non-specificity ground many structures of catalyzed oxidation of energy, and as highly toxic phenolic compound and derivative, arylamine and derivative, polycyclic aromatic hydrocarbons etc., existing more application in environmental pollution improvement.The katalysis of organic pollutant is to realize by collaborative transmission electronics of 4 cupric ions on the enzyme molecule and variation of valence in the laccase catalyzed degradation water, when substrate absorbs electronics the oxygen molecule the water is being reduced into water.Compare with other method, laccase catalytic oxidation energy consumption is low, degradation efficiency is high, easy to operate, use range is wide, do not produce excess sludge, simultaneously the multiple organic pollutant of catalysis is a biologic treating technique that has a extensive future.It is a lot of to influence laccase catalyzed oxidation organic pollutant factor active and stability.Some property of protein of laccase itself are not as reusing, surrounding environment (as factors such as the concentration of salt, pH, temperature) high susceptibility etc. having been limited effective use of laccase.In order to improve the stability of laccase, strengthen immunity from interference, it is a research focus in the present enzyme engineering field that laccase is carried out immobilization.Immobilization laccase has prolonged the work-ing life of laccase, but behind the enzyme immobilization, laccase molecule space degree of freedom is restricted, and directly has influence on the positioning action of active centre to substrate; Inside diffusional resistance descends the enzymic activity that causes near being obstructed in substrate molecule and active centre.The access times of immobilized enzyme are also relevant with the resultant of enzymic catalytic reaction with efficient.Discover that laccase is realized dechlorination fast and effectively to orthomonochlorphenol in the water and P-Chlorophenol, but laccase may generate and is difficult to biodegradable a small amount of toxicity intermediate product in reaction process, it easily is adsorbed on the laccase surface, thereby makes enzyme deactivation; Laccase is not high for the metabolic activity of part organic pollutant (as m-Chlorophenol, high chloro aldehydes matter) simultaneously, is difficult to degraded effectively fast.These effects limit the range of application of laccase, also reduced simultaneously the effect of laccase catalyzed oxidation organic pollutant.
Therefore, we propose a kind of immobilization laccase and modify PbO
2Electrode by the electric field inrichment, reduces the inside diffusional resistance of substrate molecule near the immobilization laccase active centre on the one hand, improves the enzyme liberating ability; The not high advantage of performance electrochemical oxidation organism selectivity, the part organic pollutant (as m-Chlorophenol) that laccase is difficult to the efficient catalytic degraded carries out electrochemical oxidation, and oxidation products can further be degraded by the laccase efficient catalytic; Utilize the efficient catalytic effect of laccase on the other hand, make the rapid oxidation of organic pollutant in the water, can remedy the high defective of electrochemical oxidation energy consumption for organic pollutant.
Summary of the invention
The objective of the invention is: prepare a kind of highly active laccase modified electrode, and utilize the chlorophenol pollutants in this electrode catalyst oxidizing water.
Purpose of the present invention is achieved through the following technical solutions:
A kind of laccase modified electrode is a carrier with the titanium material, is followed successively by tin-antimony oxide bottom, α-PbO from the inside to the outside by the titanium matrix surface
2Fluorine-containing β-the PbO of middle layer, a kind of reactive metal that mixes (as bismuth, nickel, lanthanum, cerium, erbium)
2Upper layer, chitosan-immobilized laccase decorative layer.
A kind of preparation method of laccase modified electrode, this method comprise three steps: electrode materials (electrode tin-antimony oxide bottom, α-PbO
2Fluorine-containing β-the PbO of middle layer, a kind of reactive metal that mixes (as bismuth, nickel, lanthanum, cerium, erbium)
2Upper layer) preparation, the preparation of chitosan-immobilized laccase, immobilization laccase are in the modification of electrode surface.Concrete steps are as follows:
(1) preparation of electrode materials
Earlier with after the titanium matrix acid etch, utilize tin tetrachloride and butter of antimony butanols mixing solutions coated titanium matrix surface, naturally after drying, 105-120 ℃ dry 10-30 minute down, by this step, repetitive coatings and dry 2-4 time, again in 500-550 ℃ of following pyrolytic decomposition 2-4 hour, naturally cool to room temperature, according to above step, repetitive coatings, drying and pyrolytic decomposition at least 2 times; Then with it as anode, galvanic deposit α-PbO in being dissolved with the sodium hydroxide electroplate liquid (A) of PbO
2Middle layer, depositing time are 0.5-1 hour, and depositing temperature is 20-50 ℃, and the anodic current density of galvanic deposit is 5-15mA/cm
2After floating thing is removed in washing, with it as anode, in the acid fluorine-containing lead solution (B) that is mixed with a kind of reactive metal (as bismuth, nickel, lanthanum, cerium, erbium), the mix fluorine-containing β-PbO of a kind of reactive metal (as bismuth, nickel, lanthanum, cerium, erbium) of galvanic deposit
2Upper layer, depositing time are 0.5-1 hour, and depositing temperature is 20-50 ℃, and the anodic current density of galvanic deposit is 5-15mA/cm
2
(2) preparation of chitosan-immobilized laccase
With the glutaraldehyde solution of chitosan and 1%-8% massfraction according to the ratio of 1g/100mL at 25 ℃ of-55 ℃ of following uniform mixing and stir more than 2 hours, after leaving standstill 8-12 hour under 4 ℃ of conditions, utilize the unnecessary glutaraldehyde solution of washed with de-ionized water 3-5 time, the suction filtration drying makes the chitin carrier of aldehyde radical in the grafting; With this carrier and the laccase thorough mixing that is dissolved in phosphoric acid salt citric acid mixing buffered soln, at pH is that 4.0-6.0, temperature are to stir 8-24 hour under the 4-55 ℃ of condition, after leaving standstill 8-12 hour under 4 ℃ of conditions, utilizing pH is that 3.5 phosphoric acid salt citric acid mixing buffered soln repeatedly washs, there is not resolvase to detect up to washings, make chitosan-immobilized laccase through vacuum-drying again, wherein, with chitin carrier blended laccase quality be the 3-7% of chitin carrier quality.
(3) immobilization laccase is in the modification of electrode surface
The chitosan-immobilized laccase and the 5% Nafion coating solution thorough mixing that will make according to step (2) drip this mixing solutions and are applied to the electrode material surface that obtains in the step (1), in the room temperature dry 1-2 hour.
Tin tetrachloride among the described electrode materials preparation method and butter of antimony butanols mixing solutions consist of the SnCl of 440-520mmol/L
45H
2The SbCl of O, 90-170mmol/L
3, the 8-12 parts by volume the concentrated hydrochloric acid, the propyl carbinol of 35-45 parts by volume of 36-38wt%; Be dissolved with the PbO that consists of 0.10-0.12mol/L of PbO sodium hydroxide electroplate liquid (A), the sodium hydroxide of 120-150g/L; Be mixed with a kind of reactive metal (as bismuth, nickel, lanthanum, cerium, erbium) acid fluorine-containing lead solution (B) consist of 0.4-0.6mol/L Pb (NO
3)
2, 0.08-0.12mol/L nitric acid, 0.005-0.04mol/L KF, 0.002-0.05mol/L reactive metal (as bismuth, nickel, lanthanum, cerium, erbium) nitrate.The blending ratio of described chitosan-immobilized laccase and 5%Nafion coating solution is 10-20g/100mL.
A kind of method of removing chlorophenol pollutants in the water, modifying the ti-supported lead dioxide electric pole that contains a kind of reactive metal (as bismuth, nickel, lanthanum, cerium or erbium) and fluorine with chitosan-immobilized laccase is anode, titanium plate, stainless steel electro-conductive material are as negative electrode, under the situation of energising, the chlorophenol pollutants in the water is oxidized.Apply the voltage of 2-2.3V between the anode and cathode, the initial pH value of institute's treating water is 3-5.
Characteristics of the present invention are:
(1) prepared laccase modified electrode is a carrier with the titanium material, is followed successively by tin-antimony oxide bottom, α-PbO from the inside to the outside by the titanium matrix surface
2Fluorine-containing β-the PbO of middle layer, a kind of reactive metal that mixes (as bismuth, nickel, lanthanum, cerium, erbium)
2Upper layer, chitosan-immobilized laccase decorative layer.
(2) prepared laccase modified electrode cost is low, in the oxidizing water chlorophenol active high, electrode life is long.
(3) adopt chlorophenol pollutants in the prepared laccase modified electrode oxidizing water, technology is simple, and is low to the operational management requirement, is applicable to that small-scale and decentralized waste water reach to water treatment.
Embodiment
Below with specific embodiment embodiment is described.
Example 1
A kind of novel laccase enzyme modified electrode, the preparation method mainly comprises three steps:
(1) preparation of electrode materials
With 15cm
2The titanium plate put into 10% oxalic acid solution, etching 2h under little situation of boiling utilizes the washed with de-ionized water surface after the taking-up; Utilize tin tetrachloride and butter of antimony butanols mixing solutions (485mmol/L SnCl
45H
2O, 130mmol/L SbCl
3, the concentrated hydrochloric acid of 10mL 36-38wt%, 40mL propyl carbinol) the coated titanium matrix surface, naturally after drying, drying is 15 minutes under 120 ℃, by this step, repetitive coatings and dry 2 times in 500 ℃ of following pyrolytic decompositions 2 hours, naturally cool to room temperature again, according to above step, repetitive coatings, drying and pyrolytic decomposition 4 times; Then with it as anode, the titanium plate is as negative electrode, is dissolved with galvanic deposit α-PbO in the electroplate liquid (A) of 0.11mol/L PbO and 140g/L sodium hydroxide at 100mL
2Middle layer, depositing time are 1 hour, and depositing temperature is 40 ℃, and the anodic current density of galvanic deposit is 10mA/cm
2After floating thing was removed in washing, as anode, the titanium plate was mixed with 0.004mol/L Erbium trinitrate, 0.5mol/L Pb (NO as negative electrode at 100mL with it
3)
2, 0.1mol/L nitric acid, 0.005mol/L KF electroplate liquid (B) in galvanic deposit β-PbO
2Upper layer, depositing time are 1 hour, and depositing temperature is 20 ℃, and the anodic current density of galvanic deposit is 10mA/cm
2, promptly get the ti-supported lead dioxide electric pole that contains a kind of reactive metal (as bismuth, nickel, lanthanum, cerium or erbium) and fluorine.
(2) preparation of chitosan-immobilized laccase
With the glutaraldehyde solution of chitosan and 5% massfraction according to the ratio of 1g/100mL at 25 ℃ of following uniform mixing and stirred 12 hours, after leaving standstill 8 hours under 4 ℃ of conditions, utilize the unnecessary glutaraldehyde solution of washed with de-ionized water 5 times, the suction filtration drying makes the chitin carrier of aldehyde radical in the grafting; With this carrier and the laccase thorough mixing that is dissolved in phosphoric acid salt citric acid mixing buffered soln, be 5.0 at pH, temperature is to stir 8 hours under 25 ℃ of conditions, after leaving standstill 8 hours under 4 ℃ of conditions, utilizing pH is that 3.5 phosphoric acid salt citric acid mixing buffered soln repeatedly washs, there is not resolvase to detect up to washings, make chitosan-immobilized laccase through vacuum-drying again, wherein, with chitin carrier blended laccase quality be 7% of chitin carrier quality.
(3) immobilization laccase is in the modification of electrode surface
The chitosan-immobilized laccase 0.08g and the 5%Nafion coating solution 0.8mL thorough mixing that will make according to step (2) drip this mixing solutions and are applied to the electrode material surface that obtains in the step (1), in the room temperature dry 2 hours.
Adopt this electrode as 2 in the anodic oxidation water, 4-two chlorophenols, negative electrode are the titanium plate, and annode area and cathode area are 15cm
2, interpole gap 15mm, received current intensity is 0.2mA/cm
2, voltage 2.2-2.3V.2,4-dichloro phenol solution starting point concentration is 37.97mg/L, and volume is 180mL, and initial pH is 4.5, and ionogen is a 0.02mol/L sodium sulfate, after 180min is carried out in reaction, and 2,4-two chlorophenol concentration are 13.88mg/L, clearance reaches 63.4%.
Example 2
Laccase modified electrode preparation method such as example 1, different is to drip behind chitosan-immobilized laccase 0.2g and the 5%Nafion coating solution 1mL thorough mixing to be applied to electrode surface.Adopt this electrode as 2 in the anodic oxidation water, 4-dichloro phenol method such as example 1, different is that received current intensity is 0.06-0.07mA/cm
2, voltage 2.0V, 2,4-dichloro phenol solution starting point concentration is 33.93mg/L, after 180min is carried out in reaction, 2,4-two chlorophenol concentration are 19.70mg/L, clearance reaches 41.9%, after 540min is carried out in reaction, 2,4-two chlorophenol concentration are 8.05mg/L, clearance reaches 76.4%.
Example 3
Laccase modified electrode preparation method such as example 1, different is to drip behind chitosan-immobilized laccase 0.1g and the 5%Nafion coating solution 0.5mL thorough mixing to be applied to electrode surface.Adopt this electrode as 2 in the anodic oxidation water, 4-dichloro phenol method such as example 2, after 180min is carried out in reaction, 2,4-two chlorophenol concentration are 21.30mg/L, and clearance reaches 37.2%, after 540min is carried out in reaction, 2,4-two chlorophenol concentration are 8.54mg/L, and clearance reaches 74.8%.
Claims (7)
1. a laccase modified electrode is characterized in that, is carrier with the titanium material, is followed successively by tin-antimony oxide bottom, α-PbO from the inside to the outside by the titanium matrix surface
2Fluorine-containing β-the PbO of middle layer, a kind of reactive metal that mixes (as bismuth, nickel, lanthanum, cerium, erbium)
2Upper layer, chitosan-immobilized laccase decorative layer.
2. the preparation method of the described laccase modified electrode of claim 1, this method comprises three steps: electrode materials (electrode tin-antimony oxide bottom, α-PbO
2Fluorine-containing β-the PbO of middle layer, a kind of reactive metal that mixes (as bismuth, nickel, lanthanum, cerium, erbium)
2Upper layer) preparation, the preparation of chitosan-immobilized laccase, immobilization laccase are in the modification of electrode surface.Concrete steps are as follows:
(1) preparation of electrode materials
After titanium matrix acid etch, utilize tin tetrachloride and butter of antimony butanols mixing solutions coated titanium matrix surface, naturally after drying, 105-120 ℃ dry 10-30 minute down, by this step, repetitive coatings and dry 2-4 time, again in 500-550 ℃ of following pyrolytic decomposition 2-4 hour, naturally cool to room temperature, according to above step, repetitive coatings, drying and pyrolytic decomposition at least 2 times; Then with it as anode, galvanic deposit α-PbO in being dissolved with the sodium hydroxide electroplate liquid (A) of PbO
2Middle layer, depositing time are 0.5-1 hour, and depositing temperature is 20-50 ℃, and the anodic current density of galvanic deposit is 5-15mA/cm
2After floating thing is removed in washing, with it as anode, in the acid fluorine-containing lead solution (B) that is mixed with a kind of reactive metal (as bismuth, nickel, lanthanum, cerium, erbium), the mix fluorine-containing β-PbO of a kind of reactive metal (as bismuth, nickel, lanthanum, cerium, erbium) of galvanic deposit
2Upper layer, depositing time are 0.5-1 hour, and depositing temperature is 20-50 ℃, and the anodic current density of galvanic deposit is 5-15mA/cm
2
(2) preparation of chitosan-immobilized laccase
With the glutaraldehyde solution of chitosan and 1%-8% massfraction according to the ratio of 1g/100mL at 25 ℃ of-55 ℃ of following uniform mixing and stir more than 2 hours, after leaving standstill 8-12 hour under 4 ℃ of conditions, utilize the unnecessary glutaraldehyde solution of washed with de-ionized water 3-5 time, the suction filtration drying makes the chitin carrier of aldehyde radical in the grafting; With this carrier and the laccase thorough mixing that is dissolved in phosphoric acid salt citric acid mixing buffered soln, at pH is that 4.0-6.0, temperature are to stir 8-24 hour under the 4-55 ℃ of condition, after leaving standstill 8-12 hour under 4 ℃ of conditions, utilizing pH is that 3.5 phosphoric acid salt citric acid mixing buffered soln repeatedly washs, there is not resolvase to detect up to washings, make chitosan-immobilized laccase through vacuum-drying again, wherein, with chitin carrier blended laccase quality be the 3-7% of chitin carrier quality.
(3) immobilization laccase is in the modification of electrode surface
The chitosan-immobilized laccase and the 5% Nafion coating solution thorough mixing that will make according to step (2) drip this mixing solutions and are applied to the electrode material surface that obtains in the step (1), in the room temperature dry 1-2 hour.
3. according to the described preparation method of claim 2, it is characterized in that described tin tetrachloride and butter of antimony butanols mixing solutions consist of the SnCl of 440-520mmol/L
45H
2The SbCl of O, 90-170mmol/L
3, the 36-38wt% concentrated hydrochloric acid of 8-12 parts by volume, the propyl carbinol of 35-45 parts by volume.
4. according to the described preparation method of claim 2, it is characterized in that, be dissolved with the PbO that consists of 0.10-0.12mol/L of the sodium hydroxide electroplate liquid (A) of PbO, the sodium hydroxide of 120-150g/L.
5. according to the described preparation method of claim 2, it is characterized in that, be mixed with a kind of reactive metal (as bismuth, nickel, lanthanum, cerium, erbium) acid fluorine-containing lead solution (B) consist of 0.4-0.6mol/L Pb (NO
3)
2, 0.08-0.12mol/L nitric acid, 0.005-0.04mol/L KF, 0.002-0.05mol/L reactive metal (as bismuth, nickel, lanthanum, cerium, erbium) nitrate.
6. according to the described preparation method of claim 2, it is characterized in that the blending ratio of described chitosan-immobilized laccase and 5% Nafion coating solution is 10-20g/100mL.
7. method of removing chlorophenol in the water, it is characterized in that, modifying the ti-supported lead dioxide electric pole that contains a kind of reactive metal (as bismuth, nickel, lanthanum, cerium or erbium) and fluorine with chitosan-immobilized laccase is anode, titanium plate, stainless steel electro-conductive material are as negative electrode, between anode and cathode, apply the voltage of 2-2.3V, the initial pH value of institute's treating water is 3-5, under agitation condition with the chlorophenol oxidation.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101638253B (en) * | 2009-09-08 | 2011-03-30 | 北京师范大学 | Method for treating waste water polluted by composite chlorophenol with coordination of visible light-laccase |
| CN102219338A (en) * | 2011-04-15 | 2011-10-19 | 北京师范大学 | Method for removing organic contaminants in water through electrochemical oxidation and biological enzyme catalyzing |
| CN104237342A (en) * | 2014-04-11 | 2014-12-24 | 北京化工大学 | Preparation method of graphite-based cerium-doped beta-PbO2 electrode and application of graphite-based cerium-doped beta-PbO2 electrode |
| CN104549176A (en) * | 2014-11-26 | 2015-04-29 | 南京航空航天大学 | Porous adsorption film and preparation method thereof |
| CN104973676A (en) * | 2014-04-10 | 2015-10-14 | 中国石油化工股份有限公司 | Composite anode electrode, preparation method and application thereof |
| CN105576142A (en) * | 2013-01-11 | 2016-05-11 | 林振坤 | Preparation method of modified indium tin oxide anode |
| CN107902729A (en) * | 2017-11-17 | 2018-04-13 | 吉林大学 | A kind of titanium-based mixes lanthanum lead dioxide electrode and preparation method thereof |
| CN108914122A (en) * | 2018-07-30 | 2018-11-30 | 山东龙安泰环保科技有限公司 | A kind of preparation method of ti-lead dioxide anode |
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2009
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101638253B (en) * | 2009-09-08 | 2011-03-30 | 北京师范大学 | Method for treating waste water polluted by composite chlorophenol with coordination of visible light-laccase |
| CN102219338A (en) * | 2011-04-15 | 2011-10-19 | 北京师范大学 | Method for removing organic contaminants in water through electrochemical oxidation and biological enzyme catalyzing |
| CN105576142A (en) * | 2013-01-11 | 2016-05-11 | 林振坤 | Preparation method of modified indium tin oxide anode |
| CN105576142B (en) * | 2013-01-11 | 2017-07-14 | 张哲夫 | A kind of preparation method for modifying indium-tin oxide anode |
| CN104973676A (en) * | 2014-04-10 | 2015-10-14 | 中国石油化工股份有限公司 | Composite anode electrode, preparation method and application thereof |
| CN104237342A (en) * | 2014-04-11 | 2014-12-24 | 北京化工大学 | Preparation method of graphite-based cerium-doped beta-PbO2 electrode and application of graphite-based cerium-doped beta-PbO2 electrode |
| CN104549176A (en) * | 2014-11-26 | 2015-04-29 | 南京航空航天大学 | Porous adsorption film and preparation method thereof |
| CN107902729A (en) * | 2017-11-17 | 2018-04-13 | 吉林大学 | A kind of titanium-based mixes lanthanum lead dioxide electrode and preparation method thereof |
| CN107902729B (en) * | 2017-11-17 | 2020-02-07 | 吉林大学 | Titanium-based lanthanum-doped lead dioxide electrode and preparation method thereof |
| CN108914122A (en) * | 2018-07-30 | 2018-11-30 | 山东龙安泰环保科技有限公司 | A kind of preparation method of ti-lead dioxide anode |
| CN108914122B (en) * | 2018-07-30 | 2020-11-27 | 山东龙安泰环保科技有限公司 | Preparation method of titanium-based lead dioxide anode |
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Application publication date: 20090603 |