CN102899683A - Preparation method of Ti-based nano-CeO2/PbO2 modified electrode - Google Patents
Preparation method of Ti-based nano-CeO2/PbO2 modified electrode Download PDFInfo
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- CN102899683A CN102899683A CN2012103550589A CN201210355058A CN102899683A CN 102899683 A CN102899683 A CN 102899683A CN 2012103550589 A CN2012103550589 A CN 2012103550589A CN 201210355058 A CN201210355058 A CN 201210355058A CN 102899683 A CN102899683 A CN 102899683A
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- pbo2
- rare earth
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Abstract
The invention relates to a preparation method of a rare earth oxide cerium oxide (Ce2O3) modified high catalytic activity Ti-based nano-PbO2 modified electrode material. One of the key issues involved is preparation of a rare earth cerium oxide (Ce2O3) modified lead electrode material. The invention employs an electrodeposition process and selects a rare earth oxide cerium oxide to modify a Ti/PbO2 metal oxide electrode. The method provided in the invention comprises: first, during preparation of a titanium-based PbO2 electrode, in an alkaline electroplating solution, conducting electroplating firstly at a high current density and then at a small current density to get a transition layer, i.e. an alpha-PbO2 layer, next, in an acidic electroplating solution, electroplating beta 3-PbO2 having catalytic activity on the well electroplated alpha-PbO2 layer, and finally in a dilute nitric acid solution containing rare earth cerium nitrate, employing a cyclic voltammetric electroplating process to modify a Ti/PbO2 electrode, thus obtaining the cerium oxide (Ce2O3)-doped and modified high catalytic activity Ti/PbO2-Ce2O3 modified electrode material.
Description
Technical field
The invention belongs to the electrode materials preparation field, relate to a kind of rare earth oxide-cerium oxide (CeO for preparing
2) the high catalytic activity Ti base nanometer PbO of modification
2Modified electrode material preparation method.
Background technology
Along with the greenization requirement to chemical synthesising technology is more and more higher, the organic electrochemistry synthetic technology is high with its efficient, the little various countries that just enjoying of pollution pay close attention to.But realize large-scale industrial production, its core is to have high performance electrode materials, the quality of electrode materials not only directly affects selectivity and the speed of reaction of reaction, and the energy consumption of influence process, is determining technology and the economy of whole Organic Electricity building-up process.
At present, mainly use Pb oxide compound or Pb alloyed oxide as anode material during organic electrochemistry is synthesized in sulfuric acid medium, but the catalytic activity of Pb metal oxide anode in sulfuric acid medium and stability current efficiency and productive rate poor, electrochemical reaction process are all lower.In order to improve the problem of Pb or Pb alloyed oxide anode, adopt take metal titanium as body material, PbO
2Be active material, preparation titanium base PbO
2Active electrode material is as anode material.Be characterized in prepared metal oxide anode material, at Cl
-, ClO
3-, NO
3-, SO
4 2-And all very stable in the diluted acid medium, its conductivity is better than graphite, and PbO
2Hardness is large, and is wear-resistant and cost is low.If it is carried out further modification, prepared electrode catalyst performance and chemical property will improve greatly, can fundamentally solve present Ti/PbO
2The problems such as electrode inactivation, the electrocatalysis characteristic that metal oxide electrode exists is poor.
Summary of the invention
The present invention relates to a kind of rare earth oxide-cerium oxide (CeO for preparing
2) the high catalytic activity Ti base nanometer PbO of modification
2Modified electrode material preparation method, one of related key issue are preparation rare earth cerium oxide (CeO
2) modification the lead electrode material.The present invention adopts electrodip process, selects rare earth oxide-cerium oxide modification Ti/PbO
2Metal oxide electrode is at first at preparation titanium base PbO
2During electrode, in the alkaline electro plating bath, first by high current density, by low current density, obtain first transition layer α-PbO afterwards
2, subsequently in acid electroplating liquid, at the good α-PbO of plating
2Plate again the β-PbO with catalytic activity on the layer
2, last at the dilute nitric acid solution that contains cerous nitrate on the rare earth, adopt the cyclic voltammetric electrochemical plating to Ti/PbO
2Electrode carries out modification, obtains cerium oxide (CeO
2) the high catalytic activity Ti/PbO of doping vario-property
2-CeO
2The modified electrode material.
Convenient and swift method prepares rare earth oxide-cerium oxide (CeO
2) the high catalytic activity Ti base nanometer PbO of modification
2The modified electrode material takes following technical scheme to realize:
The Ti matrix of (1) at first inciting somebody to action with 250 orders, 600 orders and 1000 order sand paperings polishing, makes it to present argenteous metalluster respectively.The purpose of polishing is to make Rough Metal Surface smooth, smooth.Then rinse well with distilled water, dehydrated alcohol, use again hydrofluoric acid clean.With acetone deoiling, dehydrated alcohol flushing, remove the greasy dirt of Ti matrix surface subsequently.
(2) in the alkaline electro plating bath, first by high current density, by low current density, obtain first transition layer α-PbO afterwards
2The alkaline electro plating bath forms: 0.1～0.4molL
-1PbO+2.5molL
-1NaOH, the electrode after above-mentioned steps processed places PbO to be dissolved in the saturated solution of NaOH solution, temperature is 35～40 ℃, current density is 0.3～0.5Adm
-2, electroplating time 60～120min, process can be done negative electrode with pure stereotype for this reason.
(3) in acid electroplating liquid, at the good α-PbO of plating
2Plate again the β-PbO with catalytic activity on the layer
2Acid electroplating liquid forms: 0.2molL
-1HNO
3, 0.02～0.04molL
-1NaF, the 0.65mol/l lead nitrate, current density is 5～6Adm
-2Lower plating 1～2h.
(4) at the solution that contains the rare earth cerous nitrate, adopt the cyclic voltammetric electrochemical plating to Ti/PbO
2Electrode carries out modification, obtains cerium oxide (CeO
2) the high catalytic activity Ti/PbO of doping vario-property
2-CeO
2The modified electrode material
Wherein: described at the alkaline electro plating bath, first by high current density, by low current density, obtain first transition layer α-PbO afterwards
2Layer, bath voltage is 1～2V.
Described Ti plates the β-PbO2 with catalytic activity again on the good α of plating-PbO2 layer in acid electroplating liquid, bath voltage is 2～3V.
Described solution containing the rare earth cerous nitrate, cerous nitrate content are cerous nitrate 0.5～1mol/l.
Described Ti metal adopts the pure titanium metal (purity is 99.5%) of TA1 type.
Described ethanol is dehydrated alcohol and the treating processes that removes minor amount of water through the 4A molecular sieve.
Described cyclic voltammetry sweep limit is 0～2V, and scanning speed is 0.05～0.1Vs-1, the scanning number of turns 20～60.
Embodiment
Embodiment 1
1, at first with the Ti matrix of 2cm * 2cm * 5mm respectively with 250 orders, 600 orders and 1000 order sand paperings polishing, make it to present argenteous metalluster.Then clean with distilled water flushing, use again hydrofluoric acid clean, carry out subsequently the ultrasonic irrigation of 20min with acetone, dehydrated alcohol, remove the greasy dirt of Ti matrix surface.
2, cleaned titanium sheet is put into electrolyzer as anode, the pure stereotype of 4cm * 4cm * 5mm is done negative electrode, at 0.1molL
-1PbO+2.5molL
-1The alkaline electro plating bath of NaOH, voltage 1V, temperature is 35 ℃, electroplating time 60min electroplates first transition layer α-PbO in the Ti metallic surface
2
3, will plate good Ti/ α-PbO
2Be placed on 0.2molL
-1HNO
3+ 0.02molL
-1In the NaF+0.65mol/l lead nitrate acid electroplating liquid, the pure stereotype of 4cm * 4cm * 5mm is done negative electrode, is plating α-PbO
2The surface plate again β-PbO that one deck has catalytic activity
2, bath voltage is 2V, electroplates 2h.
4, the Ti/ β-PbO that the 3rd step was made
2Be placed on the solution of 0.5mol/l cerous nitrate, adopting the cyclic voltammetry sweep limit is 0～2V, and scanning speed is 0.05Vs
-1Electrode is carried out rare-earth-doped modification, and scanning 20 circles namely obtain Ti/CeO
2-PbO
2
Embodiment 2
1, at first with the Ti matrix of 2cm * 2cm * 5mm respectively with 250 orders, 600 orders and 1000 order sand paperings polishing, make it to present argenteous metalluster.Then clean with distilled water flushing, use again hydrofluoric acid clean, carry out subsequently the ultrasonic irrigation of 20min with acetone, dehydrated alcohol, remove the greasy dirt of Ti matrix surface.
2, cleaned titanium sheet is put into electrolyzer as anode, the pure stereotype of 4cm * 4cm * 5mm is done negative electrode, at 0.2molL
-1PbO+2.5molL
-1The alkaline electro plating bath of NaOH, voltage 2V, temperature is 35 ℃, electroplating time 90min electroplates first transition layer α-PbO in the Ti metallic surface
2
3, will plate good Ti/ α-PbO
2Be placed on 0.2molL
-1HNO
3+ 0.03molL
-1In the NaF+0.65mol/l lead nitrate acid electroplating liquid, the pure stereotype of 4cm * 4cm * 5mm is done negative electrode, at the good α-PbO of plating
2The surface plate again β-PbO that one deck has catalytic activity
2Bath voltage is 3V, electroplates 2h.
4, the Ti/ β-PbO that the 3rd step was made
2Be placed on the solution of 0.5mol/l cerous nitrate, adopting the cyclic voltammetry sweep limit is 0～2V, and scanning speed is 0.05Vs
-1Electrode is carried out rare-earth-doped modification, and scanning 20 circles namely obtain Ti/CeO
2-PbO
2
Embodiment 3
1, at first with respectively 250 orders, 600 orders and the 1000 order sand paperings polishing of Ti matrix of 2cm * 2cm * 5mm, makes it to present argenteous metalluster.Then clean with distilled water flushing, use again hydrofluoric acid clean, carry out subsequently the ultrasonic irrigation of 20min with acetone, dehydrated alcohol, remove the greasy dirt of Ti matrix surface.
2, cleaned titanium sheet is put into electrolyzer as anode, the pure stereotype of 4cm * 4cm * 5mm is done negative electrode, at 0.3molL
-1PbO+2.5molL
-1The alkaline electro plating bath of NaOH, voltage 2V, temperature is 35 ℃, electroplating time 120min electroplates first transition layer α-PbO in the Ti metallic surface
2
3, will plate good Ti/ α-PbO
2Be placed on 0.2molL
-1HNO
3+ 0.04molL
-1In the NaF+0.65mol/l acid electroplating liquid, the pure stereotype of 4cm * 4cm * 5mm is done negative electrode, at the good α-PbO of plating
2The surface plate again β-PbO that one deck has catalytic activity
2Bath voltage is 3V, electroplates 1.5h.
4, the Ti/ β-PbO that the 3rd step was made
2Be placed on the solution of 1mol/l cerous nitrate, adopting the cyclic voltammetry sweep limit is 0～2V, and scanning speed is 0.05Vs
-1Electrode is carried out rare-earth-doped modification, and scanning 20 circles namely obtain Ti/CeO
2-PbO
2
Embodiment 4
1, at first with respectively 250 orders, 600 orders and the 1000 order sand paperings polishing of Ti matrix of 2cm * 2cm * 5mm, makes it to present argenteous metalluster.Then clean with distilled water flushing, use again hydrofluoric acid clean, carry out subsequently the ultrasonic irrigation of 20min with acetone, dehydrated alcohol, remove the greasy dirt of Ti matrix surface.
2, cleaned titanium sheet is put into electrolyzer as anode, the pure stereotype of 4cm * 4cm * 5mm is done negative electrode, at 0.4molL
-1PbO+2.5molL
-1The alkaline electro plating bath of NaOH, voltage 2V, temperature is 40 ℃, electroplating time 120min electroplates first transition layer α-PbO in the Ti metallic surface
2
3, will plate good Ti/ α-PbO
2Be placed on 0.2molL
-1HNO
3+ 0.04molL
-1In the NaF+0.65mol/l lead nitrate acid electroplating liquid, the pure stereotype of 4cm * 4cm * 5mm is done negative electrode, is plating α-PbO
2The surface plate again β-PbO that one deck has catalytic activity
2Bath voltage is 3V, electroplates 1.5h.
4, the Ti/ β-PbO that the 3rd step was made
2Be placed on the solution of 1mol/l cerous nitrate, adopting the cyclic voltammetry sweep limit is 0～2V, and scanning speed is 0.1Vs
-1Electrode is carried out rare-earth-doped modification, and scanning 60 circles namely obtain Ti/CeO
2-PbO
2
Embodiment 5
1, at first with the Ti matrix of 2cm * 2cm * 5mm respectively with 250 orders, 600 orders and 1000 order sand paperings polishing, make it to present argenteous metalluster.Then clean with distilled water flushing, use again hydrofluoric acid clean, carry out subsequently the ultrasonic irrigation of 20min with acetone, dehydrated alcohol, remove the greasy dirt of Ti matrix surface.
2, cleaned titanium sheet is put into electrolyzer as anode, the pure stereotype of 4cm * 4cm * 5mm is done negative electrode, at 0.4molL
-1PbO+2.5molL
-1The alkaline electro plating bath of NaOH, voltage 1.5V, temperature is 40 ℃, electroplating time 90min electroplates first transition layer α-PbO in the Ti metallic surface
2
3, will plate good Ti/ α-PbO2 and be placed on 0.2molL
-1HNO
3+ 0.04molL
-1In the NaF+0.65mol/l lead nitrate acid electroplating liquid, the pure stereotype of 4cm * 4cm * 5mm is done negative electrode, is plating α-PbO
2The surface plate again β-PbO that one deck has catalytic activity
2Bath voltage is 2.5V, electroplates 2h.
4, the Ti/ β-PbO that the 3rd step was made
2Be placed on the solution of 1mol/l cerous nitrate, adopting the cyclic voltammetry sweep limit is 0～2V, and scanning speed is 0.05Vs
-1Electrode is carried out rare-earth-doped modification, and scanning 40 circles namely obtain Ti/CeO
2-PbO
2
Claims (6)
1. one kind prepares rare earth oxide-cerium oxide (CeO
2) the high catalytic activity Ti base nanometer PbO of modification
2Modified electrode material preparation method is characterized in that:
(1) with the Ti matrix with after the sand papering polishing, use successively distilled water, dehydrated alcohol, hydrofluoric acid clean, acetone deoiling, the dehydrated alcohol flushing is to remove the greasy dirt of Ti matrix surface;
(2) the Ti matrix of handling well is put into the alkaline electro plating bath, be equipped with cathode material, α-PbO on its plated surface
2Layer;
(3) will plate again good α-PbO
2The Ti matrix of layer is placed in the acid electroplating liquid, plates the β-PbO with catalytic activity again
2Layer;
(4) put at last the solution that contains the rare earth cerous nitrate, adopt the cyclic voltammetric electrochemical plating to Ti/PbO
2Electrode carries out modification, and the cyclic voltammetry sweep limit is 0～2V, and scanning speed is 0.05～0.1Vs
-1, obtain cerium oxide (CeO
2) the high catalytic activity Ti/PbO of doping vario-property
2-CeO
2The modified electrode material.
2. in the method for claim 1, sand paper adopts 250 orders, 600 orders and 1000 orders;
3. in the method for claim 1, the alkaline electro plating bath is by 0.1～0.4molL
-1PbO and 2.5molL
-1NaOH form; Temperature is 35～40 ℃ during plating, and current density is 0.3～0.5Adm
-2, electroplating time 60～120min; Cathode material is pure stereotype;
4. in the method for claim 1, acid electroplating liquid is by 0.2molL
-1HNO
3, 0.02～0.04molL
-1NaF and 0.65mo1L
-1Pb (NO)
2Form; Current density during plating is 5～6Adm
-2, electroplating time is 60～120min;
5. in the method for claim 1, the solution content of rare earth cerous nitrate is cerous nitrate 0.5～1mol/1;
6. in the method for claim 1, cyclic voltammetry scanning scans the number of turns 20～60.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103132076A (en) * | 2013-02-07 | 2013-06-05 | 浙江工业大学 | Lanthanum-gadolinium co-doping titanium-based lead dioxide electrode and preparation method and application thereof |
| CN103572331A (en) * | 2013-11-14 | 2014-02-12 | 昆明理工恒达科技股份有限公司 | Fence type titanium-based PbO2 anode for electrodeposition of non-ferrous metals and manufacturing method of anode |
| CN103602967A (en) * | 2013-12-03 | 2014-02-26 | 淮南师范学院 | Preparation method for novel high catalytic activity Ti/TiO2/Ce-PbO2 electrode |
| CN104561966A (en) * | 2015-01-30 | 2015-04-29 | 南京大学连云港高新技术研究院 | Preparation method of three-dimensional electrocatalytic composite electrode plate |
| CN106222717A (en) * | 2016-08-17 | 2016-12-14 | 浙江工业大学 | A kind of I2 doping lead dioxide electrode and its preparation method and application |
| CN108048867A (en) * | 2017-12-05 | 2018-05-18 | 淮南师范学院 | A kind of preparation method of novel photoelectric catalysis material electrode |
| CN108823593A (en) * | 2018-05-30 | 2018-11-16 | 中氧科技（广州）有限公司 | A kind of preparation method of the membrane electrode of rare earth doped oxide |
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Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103132076A (en) * | 2013-02-07 | 2013-06-05 | 浙江工业大学 | Lanthanum-gadolinium co-doping titanium-based lead dioxide electrode and preparation method and application thereof |
| CN103132076B (en) * | 2013-02-07 | 2015-10-07 | 浙江工业大学 | Ti-supported lead dioxide electric pole of a kind of lanthanum, gadolinium codoped and its preparation method and application |
| CN103572331A (en) * | 2013-11-14 | 2014-02-12 | 昆明理工恒达科技股份有限公司 | Fence type titanium-based PbO2 anode for electrodeposition of non-ferrous metals and manufacturing method of anode |
| CN103572331B (en) * | 2013-11-14 | 2016-08-17 | 昆明理工恒达科技股份有限公司 | The non-ferrous metal electrodeposition manufacture method of palisading type titanio PbO2 anode |
| CN103602967A (en) * | 2013-12-03 | 2014-02-26 | 淮南师范学院 | Preparation method for novel high catalytic activity Ti/TiO2/Ce-PbO2 electrode |
| CN103602967B (en) * | 2013-12-03 | 2016-04-13 | 淮南师范学院 | A kind of high catalytic activity Ti/TiO 2/ Ce-PbO 2the preparation method of electrode |
| CN104561966A (en) * | 2015-01-30 | 2015-04-29 | 南京大学连云港高新技术研究院 | Preparation method of three-dimensional electrocatalytic composite electrode plate |
| CN106222717A (en) * | 2016-08-17 | 2016-12-14 | 浙江工业大学 | A kind of I2 doping lead dioxide electrode and its preparation method and application |
| CN108048867A (en) * | 2017-12-05 | 2018-05-18 | 淮南师范学院 | A kind of preparation method of novel photoelectric catalysis material electrode |
| CN108048867B (en) * | 2017-12-05 | 2019-06-11 | 淮南师范学院 | A kind of preparation method of photoelectrocatalysimaterial material electrode |
| CN108823593A (en) * | 2018-05-30 | 2018-11-16 | 中氧科技（广州）有限公司 | A kind of preparation method of the membrane electrode of rare earth doped oxide |
| CN108823593B (en) * | 2018-05-30 | 2020-10-09 | 中氧科技（广州）有限公司 | Preparation method of rare earth oxide doped membrane electrode |
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Application publication date: 20130130 |