CN102043004B - Preparation method of PbO2 electrode with high oxygen evolution potential and long service life - Google Patents
Preparation method of PbO2 electrode with high oxygen evolution potential and long service life Download PDFInfo
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- CN102043004B CN102043004B CN 200910197160 CN200910197160A CN102043004B CN 102043004 B CN102043004 B CN 102043004B CN 200910197160 CN200910197160 CN 200910197160 CN 200910197160 A CN200910197160 A CN 200910197160A CN 102043004 B CN102043004 B CN 102043004B
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Abstract
The invention relates to a PbO2 electrode with high oxygen evolution potential and long service life and a preparation method thereof. The preparation method comprises the following steps of: pre-growing a layer of erect and orderly TiO2-NTs nanotubes, used as an interlayer, on a Ti plate by using an electrochemical anodization method; and then electrically depositing PbO2 in a lead nitrate solution containing fluorine macromolecules to prepare an F-PbO2/TiO2-NTs/Ti electrode. Compared with a traditional PbO2 electrode, the PbO2 electrode disclosed in the invention has high oxygen evolution potential of more than 2.4 V and long service life of longer than 20 years.
Description
Technical field
The present invention relates to belong to materials chemistry field and electrochemical method technical field, relate to the long-life PbO of a kind of oxygen evolution potential
2Electrode material and preparation method.
Background technology
PbO
2Electrode is to study comparatively widely a kind of anode material, and it has with low cost, and material is easy to get, and manufacture craft is also easier, and has oxygen evolution potential and high catalytic activity.But because PbO
2Relatively poor with the bonding properties of matrix, and Pb has toxicity, so these deficiencies have just limited PbO
2The application of electrode.In order to overcome these deficiencies, some researchers are with the fluorine-ion-doped PbO that arrives
2In, research finds that the doping of fluorine ion has limited PbO
2The free movement of free oxygen atom in the hydrated sheath reduces the diffusion of its anode inside, and fluorine ion has occupied the passage that the active oxygen atom anode spreads in crystal layer simultaneously, thereby the doping of fluorine ion has effectively delayed PbO
2The oxidation of the deteriorated and Ti substrate of coating, on the other hand, the fluorine ion in the hydrated sheath also is unfavorable for H
2O
2Generation, intercepted simultaneously SO
4 2-And Pb
4+Contact, suppressed PbO
2Anodic solution.Therefore, the doping of fluorine ion has prolonged PbO greatly
2The life-span of anode.With PbO
2Anode is compared, F-PbO
2Anode has larger specific surface area, and surface energy adsorbs more active oxygen species, the minimizing of the active oxygen species that cause in the existence of to a certain degree having offset owing to F-.Simultaneously, at anode surface because the free movement of free oxygen atom and all be subject to the F-restriction to the diffusion of electrode interior, thereby cause that more OH free radical accumulation is arranged, therefore improved F-PbO
2Electrocatalysis Degradation ability to organic contaminant.
Because the Ti metal has good anti-corrosive properties, cheap price, thermal conductivity is little, the surface is easy to the advantages such as physics and chemistry processing processings, is to prepare the desirable matrix material of oxide electrode.Studies show that Ti base PbO
2Electrode has good corrosion resistance and electric conductivity, and have oxygen evolution potential higher, process the organic contaminant ability stronger advantage, so this electrode is having a wide range of applications aspect electrolytic industry and the environmental treatment.But at preparation Ti/PbO
2It is found that during electrode, at Ti and PbO
2Resistance on the interface is larger, and adhesion a little less than, it is active and stable to have affected electrode electro Chemical.For addressing this problem, a kind of method is at Ti substrates Ag, Au, then prepares PbO at Ti
2Second method is to prepare the good oxide membranous layer of electric conductivity at Ti first, as contains SnO
2, Sb
2O
5Rete, then on this film, prepare PbO with thermosetting or electrodeposition process
2
Summary of the invention
Purpose of the present invention is exactly to provide a kind of oxygen evolution potential long-life PbO for the defective that overcomes above-mentioned prior art existence
2Electrode and preparation method.
Purpose of the present invention can be achieved through the following technical solutions: the long-life PbO of a kind of oxygen evolution potential
2Electrode and preparation method is characterized in that, the method is to adopt electrochemical deposition method, on the titanium base titania nanotube of ordering growth as the middle layer, electro-deposition PbO in containing the high molecular lead nitrate solution of fluorine
2, preparation F-PbO
2/ TiO
2-NTs electrode.
Described method specifically may further comprise the steps:
(1) with pure titanium plate surface mechanical grinding polishing, cleans up;
(2) take solute as NaF with supporting electrolyte, and add the alcohols adjuvant, solvent is water surplus, preparation electrolytic solution;
(3) the titanium sheet in the step (1) is as working electrode, and platinized platinum is to electrode, carries out electrochemical anodic oxidation and processes, and obtains upright orderly TiO at titanium-based surface
2Nanotube obtains TiO
2-NTs/Ti;
(4) with Pb (NO
3)
2, NaF, HNO
3, fluororesin is mixed with electroplate liquid, and the concentration of plumbi nitras is 0.1mol/L～1mol/L in this electroplate liquid, and the concentration of sodium fluoride is 0.01mol/L～0.05mol/L, and the concentration of nitric acid is 0.01mol/L～0.2mol/L, the concentration of fluororesin is 1～20ml/L;
(5) TiO for preparing with step (3)
2-NTs/Ti is working electrode, and platinized platinum is auxiliary electrode, and saturated calomel electrode is contrast electrode, adopts the continuous current method fluorine-containing PbO
2Deposit in the nanotube preparation F-PbO
2/ TiO
2-NTs electrode product.
Pure titanium sheet thickness in the described step (1) is 0.02～0.1mm, is of a size of 1～6cm
2
The concentration of NaF is 0.05～1.0wt% in the described step (2), and supporting electrolyte is 1.6～2.0wt%Na
2SO
4, the alcohols adjuvant is the polyglycol (PG400) of 10～50wt%.
Working electrode and be 0.5～1.0cm to electrode separation in the described step (3), anodizing voltage is 10～40V, the anodization time is 1～5h.
The concentration of plumbi nitras is 0.1mol/L～1mol/L in described step (4) electroplate liquid, and the concentration of sodium fluoride is 0.01mol/L～0.05mol/L, and the concentration of nitric acid is 0.01mol/L～0.2mol/L, and the concentration of fluororesin is 1～20ml/L;
Temperature of reaction is 60 ℃～100 ℃ in the described step (5), and deposition current is 0.03～0.05A/cm
2Sedimentation time is 0.5-2h.
The present invention adopts chemical method to prepare F-PbO take titanium-based titanium dioxide nanotube as carrier
2/ TiO
2-NTs/Ti electrode utilizes the TiO of titanium matrix surface
2PbO is improved and optimized to nanotube microcosmic solid space structure
2Eelctro-catalyst performance and stability thereof.First the TiO of preparation
2-NTs carries out the bottom deposition of bottom reduction and a small amount of Cu, then with fluorine-containing PbO
2Be assembled into wherein, on the one hand TiO
2-NTs is owing to be the nanotube tubular structure, compares with the Ti plate to have larger specific surface area, so can increase considerably fluorine-containing PbO
2The assembling amount, in addition on the one hand, TiO
2-NTs can make fluorine-containing PbO as tubular structure
2Very firmly be assembled on the matrix, this has just solved PbO
2With substrate in conjunction with unstable shortcoming.The bottom deposition of simultaneously a small amount of Cu can solve PbO
2And the bad problem of the electric conductivity between the substrate.
The present invention utilizes TiO
2The characteristics such as nanotube stereoscopic three-dimensional structure, bigger serface and high spatial rate as electrode matrix, will have the PbO of oxygen evolution potential with it
2Be assembled in the nanotube, the electrode of acquisition can not only show good electrocatalysis characteristic, and this structure can improve PbO greatly
2The stability of electrode.With conventional P bO
2, the present invention has following advantage:
1. and PbO
2Anode is compared, and the present invention takes full advantage of upright orderly TiO
2The nanotube stereoeffect has improved PbO on electrode unit's specific surface area greatly
2The charge capacity of eelctro-catalyst.Simultaneously, the PbO of anode surface
2The free movement of free oxygen atom and all be subject to all and be dispersed in the high molecular restriction of fluorine between the PbO2 crystal to the diffusion of electrode interior in the lattice, thereby greatly improved the oxygen evolution potential of electrode, reached more than the 2.4V.
Because the doping of fluorine so that in crystal layer fluorine ion occupied the passage of active oxygen atom anode diffusion, thereby effectively delayed PbO
2The oxidation of the deteriorated and Ti substrate of coating; On the other hand, the fluorine ion in the hydrated sheath also can intercept SO in the reaction medium
4 2-Deng negative ion and pb
4+Contact, can suppress PbO
2Anodic solution.What is more important the present invention has utilized upright orderly TiO
2The nanotube template, PbO
2Form a stake formula structure after entering in the pipe, this in order, the close contact of micro-scale structures, load is more even, load is more tight, does not have the crack to exist, this will strengthen the adhesion with matrix greatly, and the even tension of each binding site.And this even, tight coating can reduce the probability that causes face checking because of separating out of oxygen, so very effectively prolonged the serviceable life of electrode.
Description of drawings
The PbO of Fig. 1 the inventive method preparation
2-F-TiO
2The scanning electron microscope of-NTs/Ti electrode (SEM) photo;
The PbO of Fig. 2 the inventive method preparation
2-F-TiO
2The contact angle figure of-NTs/Ti electrode;
The PbO of Fig. 3 the inventive method preparation
2-F-TiO
2The oxygen evolution potential curve map of-NTs/Ti electrode.
Embodiment
The present invention is described in detail below in conjunction with the drawings and specific embodiments.
F-PbO
2The preparation of/Ti electrode.Described method specifically may further comprise the steps:
(1) is 0.08mm with thickness, is of a size of 3cm
2The polishing of pure titanium plate surface mechanical grinding, clean up;
(2) with 0.4mol/L Pb (NO
3)
2, 0.03mol/LNaF, 0.08mol/L HNO
3, the 6ml/L fluororesin is mixed with electroplate liquid;
(3) take the Ti of step (1) preparation as working electrode, platinized platinum is auxiliary electrode, and saturated calomel electrode (SCE) be contrast electrode, and under 80 ℃ of temperature of reaction, employing continuous current method is fluorine-containing PbO
2Deposit on the Ti plate, deposition current is 0.04A/cm
2, sedimentation time is 1h, preparation F-PbO
2/ Ti electrode electrode product.
(4) about the oxygen evolution potential 1.9V of this electrode, be about 3 years serviceable life that is obtained electrode by the accelerated aging test result calculations.
PbO
2/ TiO
2The preparation of-NTs/Ti electrode.Described method specifically may further comprise the steps:
(1) is 0.08mm with thickness, is of a size of 3cm
2The polishing of pure titanium plate surface mechanical grinding, clean up;
(2) with 0.05wt%NaF and supporting electrolyte 1.6wt%Na
2SO
4Be solute, add alcohols adjuvant 10wt% polyglycol (PG400), solvent is water surplus, preparation electrolytic solution;
(3) the titanium sheet in the step (1) is as working electrode, and platinized platinum is to electrode, working electrode and be 0.5cm to electrode separation, carrying out electrochemical anodic oxidation processes, anodizing voltage is 10V, and the anodization time is 3h, obtains upright orderly TiO at titanium-based surface
2Nano-tube array;
(4) with 0.4mol/L Pb (NO
3)
2, 0.03mol/L NaF, 0.08mol/L HNO
3, fluororesin 10ml/L is mixed with electroplate liquid;
(5) TiO for preparing with step (3)
2-NTs/Ti is working electrode, and platinized platinum is auxiliary electrode, and saturated calomel electrode is contrast electrode, under 60 ℃ of temperature of reaction, adopts the continuous current method PbO
2Deposit in the nanotube, deposition current is 0.03A/cm
2, sedimentation time is 0.5h, preparation PbO
2/ TiO
2-NTs/Ti electrode electrode product.
(6) about the oxygen evolution potential 1.8V of this electrode, be about 5 years serviceable life that is obtained electrode by the accelerated aging test result calculations.
A kind of PbO of oxygen evolution potential
2Electrode and preparation method, the method adopt electrochemical deposition method, on the titanium base titania nanotube of vertical growth as carrier, preparation F-PbO
2/ TiO
2-NTs/Ti electrode.Described method specifically may further comprise the steps:
(1) is 0.1mm with thickness, is of a size of 6cm
2The polishing of pure titanium plate surface mechanical grinding, clean up;
(2) with 1.0wt%NaF and supporting electrolyte 2.0wt%Na
2SO
4Be solute, add alcohols adjuvant 50wt% polyglycol (PG400), solvent is water surplus, preparation electrolytic solution;
(3) the titanium sheet in the step (1) is as working electrode, and platinized platinum is to electrode, working electrode and be 1.0cm to electrode separation, carrying out electrochemical anodic oxidation processes, anodizing voltage is 20V, and the anodization time is 5h, obtains upright orderly TiO at titanium-based surface
2Nano-tube array;
(4) with 0.1mol/L Pb (NO
3)
2, 0.01mol/L NaF, 0.01mol/L HNO
3, the 1ml/L fluororesin is mixed with electroplate liquid;
(5) TiO for preparing with step (3)
2-NTs/Ti is working electrode, and platinized platinum is auxiliary electrode, and saturated calomel electrode (SCE) is contrast electrode, under 100 ℃ of temperature of reaction, adopts the continuous current method fluorine-containing PbO
2Deposit in the nanotube, deposition current is 0.05A/cm
2, sedimentation time is 2h, preparation F-PbO
2/ TiO
2-NTs/Ti electrode product.
(6) the oxygen evolution potential 2.4V of this electrode, be about 25 years serviceable life that is obtained electrode by the accelerated aging test result calculations.
Embodiment 4
A kind of PbO of oxygen evolution potential
2Electrode and preparation method, the method adopt electrochemical deposition method, on the titanium base titania nanotube of vertical growth as carrier, preparation F-PbO
2/ TiO
2-NTs electrode.Described method specifically may further comprise the steps:
(1) is 0.02mm with thickness, is of a size of 1cm
2The polishing of pure titanium plate surface mechanical grinding, clean up;
(2) with 1.8wt%NaF and supporting electrolyte 2.5wt%Na
2SO
4Be solute, add alcohols adjuvant 40wt% polyglycol (PG400), solvent is water surplus, preparation electrolytic solution;
(3) the titanium sheet in the step (1) is as working electrode, and platinized platinum is to electrode, working electrode and be 1.0cm to electrode separation, carrying out electrochemical anodic oxidation processes, anodizing voltage is 40V, and the anodization time is 1h, obtains upright orderly TiO at titanium-based surface
2Nano-tube array;
(4) with 1mol/L Pb (NO
3)
2, 0.05mol/L NaF, 0.2mol/L HNO
3, the 20ml/L fluororesin is mixed with electroplate liquid;
(5) TiO for preparing with step (3)
2-NTs/Ti is working electrode, and platinized platinum is auxiliary electrode, and saturated calomel electrode (SCE) is contrast electrode, under 100 ℃ of temperature of reaction, adopts the continuous current method fluorine-containing PbO
2Deposit in the nanotube, deposition current is 0.08A/cm
2, sedimentation time is 1.5h, preparation F-PbO
2/ TiO
2-NTs/Ti electrode product.
(6) the oxygen evolution potential 2.4V of this electrode, be about 20 years serviceable life that is obtained electrode by the accelerated aging test result calculations.
The purpose of this invention is to provide a kind ofly take the orderly Nano tube array of titanium dioxide that stands on the Titanium primary surface as carrier, adopt the Chemical assembly method to prepare F-PbO
2/ TiO
2-NTs/Ti electrode is also studied its application in processing organic contaminant.
The above-mentioned description to embodiment is can understand and apply the invention for ease of those skilled in the art.The person skilled in the art obviously can easily make various modifications to these embodiment, and needn't pass through performing creative labour being applied in the General Principle of this explanation among other embodiment.Therefore, the invention is not restricted to the embodiment here, those skilled in the art should be within protection scope of the present invention for improvement and modification that the present invention makes according to announcement of the present invention.
Claims (5)
1. long-life PbO of oxygen evolution potential
2The preparation method of electrode is characterized in that, the method is to adopt electrochemical deposition method, the upright orderly TiO of pregrown one deck on the Ti plate
2-NTs nanotube is as the middle layer, then electro-deposition PbO in containing the high molecular lead nitrate solution of fluorine
2, prepare F-PbO
2/ TiO
2-NTs/Ti electrode;
Described method specifically may further comprise the steps:
(1) with pure titanium plate surface mechanical grinding polishing, cleans up;
(2) take 0.05～1.0wt%NaF and 1.6～2.0wt% supporting electrolyte as solute, add 10～50 wt% alcohols adjuvants, solvent is water surplus, preparation electrolytic solution;
(3) the titanium sheet in the step (1) is as working electrode, and platinized platinum is to electrode, carries out electrochemical anodic oxidation and processes, and obtains orderly TiO at titanium-based surface
2Nanotube obtains TiO
2-NTs/Ti;
(4) with Pb (NO
3)
2, NaF, HNO
3, fluororesin is mixed with electroplate liquid, and the concentration of plumbi nitras is 0.1 mol/L～1 mol/L in this electroplate liquid, and the concentration of sodium fluoride is 0.01mol/L～0.05 mol/L, and the concentration of nitric acid is 0.01mol/L～0.2 mol/L, the concentration of fluororesin is 1～20ml/L;
(5) TiO for preparing with step (3)
2-NTs/Ti is working electrode, and platinized platinum is auxiliary electrode, and saturated calomel electrode is contrast electrode, adopts the galvanostatic deposition method fluorine-containing PbO
2Deposit in the nanotube preparation F-PbO
2/ TiO
2-NTs/Ti electrode product.
2. the PbO of a kind of oxygen evolution potential according to claim 1
2The preparation method of electrode is characterized in that, the pure titanium sheet thickness in the described step (1) is 0.02 ~ 0.1mm, is of a size of 1 ~ 6cm
2
3. the PbO of a kind of oxygen evolution potential according to claim 1
2The preparation method of electrode is characterized in that, supporting electrolyte is Na in the described step (2)
2SO
4, the alcohols adjuvant is polyglycol (PG400).
4. the PbO of a kind of oxygen evolution potential according to claim 1
2The preparation method of electrode is characterized in that, working electrode and be 0.5～1.0cm to electrode separation in the described step (3), and anodizing voltage is 10～40V, the anodization time is 1～5h.
5. the PbO of a kind of oxygen evolution potential according to claim 1
2The preparation method of electrode is characterized in that, temperature of reaction is 60 ℃～100 ℃ in the described step (5), and deposition current is 0.03～0.05A/cm
2Sedimentation time is 0.5～2h.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102534718B (en) * | 2012-01-12 | 2015-05-20 | 沈阳化工大学 | Method for preparing PbO2-modified TiO2 nanotube electrode |
| CN104733774A (en) * | 2013-12-20 | 2015-06-24 | 苏州宝时得电动工具有限公司 | Battery |
| CN105112980A (en) * | 2015-09-30 | 2015-12-02 | 淮南师范学院 | High-activity TiO2-NTs/PbO2-Y-Co3O4 modified electrode and method for electrocatalytic oxidation treatment of pharmaceutical wastewater with same |
| CN108328703B (en) * | 2018-02-01 | 2020-11-27 | 环境保护部华南环境科学研究所 | Preparation of titanium-based titanium dioxide nanotube deposited tin-antimony-fluorine electrode and application of electrode in chromium-electroplating wastewater chromium fog inhibitor degradation |
| CN110627167A (en) * | 2019-09-27 | 2019-12-31 | 上海海事大学 | Cs-doped novel composite Ti-Net/TiO2-NTs/β-PbO2Electrode and method for producing same |
| CN111186883B (en) * | 2020-01-09 | 2021-08-24 | 青岛理工大学 | Novel preparation technology of lead dioxide electrode modified by titanium tetroxide nanotube |
| CN113061955B (en) * | 2021-03-17 | 2023-02-21 | 宜兴禹博治环保科技有限公司 | Preparation method of conductive polyaniline modified electrode |
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| CN101054684A (en) * | 2007-02-07 | 2007-10-17 | 浙江工业大学 | Method of preparing fluorine-containing lead dioxide electrode on titanium basal body |
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| JP3409920B2 (en) * | 1994-05-19 | 2003-05-26 | ペルメレック電極株式会社 | Lead dioxide electrode for electrolysis and method for producing the same |
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| CN101054684A (en) * | 2007-02-07 | 2007-10-17 | 浙江工业大学 | Method of preparing fluorine-containing lead dioxide electrode on titanium basal body |
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