CN102864465A - Preparation method of high-activity Ti/Pr2O3-PbO2 modified electrode - Google Patents

Preparation method of high-activity Ti/Pr2O3-PbO2 modified electrode Download PDF

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CN102864465A
CN102864465A CN2012103550574A CN201210355057A CN102864465A CN 102864465 A CN102864465 A CN 102864465A CN 2012103550574 A CN2012103550574 A CN 2012103550574A CN 201210355057 A CN201210355057 A CN 201210355057A CN 102864465 A CN102864465 A CN 102864465A
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pbo2
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CN102864465B (en
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王凤武
徐迈
李书东
方文彦
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Huainan Normal University
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Abstract

The invention relates to a preparation method of high-catalytic-activity Ti-based nano-PbO2-modifed electrode material modified by rare earth oxide and Pr2O3 and provides the key solution of preparing rare-earth Pr2O3 modified lead electrode material. The electrodeposition method is used, and Ti/PbO2 metal oxide electrode modified by rare earth oxide and Pr2O3 is selected. Firstly, a transition alpha-PbO2 layer is obtained in alkali electroplate liquid by high current density prior to low current density during preparation of the titanium-based PbO2 electrode; secondly, catalytically active beta-PbO2 is plated on the plated alpha-PbO2 layer in acid electroplate liquid; and thirdly, the Ti/PbO2 electrode is modified by cyclic voltammetry electroplating process in dilute nitric acid solution containing rear-earth praseodymium nitrate, and the high-catalytic-activity Ti/PbO2-Pr2O3 modified electrode material modified by doping Pr2O3 is obtained.

Description

A kind of high reactivity Ti/Pr 2O 3-PbO 2The preparation method of modified electrode
Technical field
The invention belongs to the electrode materials preparation field, relate to a kind of rare earth oxide-praseodymium sesquioxide (Pr for preparing 2O 3) the high catalytic activity Ti base nanometer PbO of modification 2Modified electrode material preparation method.
Background technology
In recent years, the Organic Electricity synthesis technique that is called as green synthesis techniques is as a kind of novel and effective chemical synthesis process is subject to people's attention day by day.Compare with traditional organic synthesis method, Organic Electricity is synthetic by this reagent that cleans most of electronics, has avoided the use of other reductive agent or oxygenant, and can operate at normal temperatures and pressures environmental friendliness; Can also by regulating voltage and electric current (density) the carrying out with the control reaction, be convenient to the automatization control of whole process.
The organic electrochemistry synthetic technology is to utilize electrochemical principle to realize that matter and energy transforms, and the surface reaction characteristic between electrode and the ionogen is core and the essential place that affects the electrochemical reaction performance.Therefore, for the organic electrochemistry reaction process, have the electrode research and development of efficient electric catalytic performance, electrolytical synthetic and electrode and the electrolytical matching optimization of excellent property is extremely important key issue during the model electrochemical reaction is researched and developed.Electrochemical techniques with cleaning realize electroorganic synthesis, the performance of electrode materials is its industrialized key factor of restriction, not only directly selectivity and the speed of reaction of impact reaction, and the energy consumption of influence process are determining technology and the economy of whole Organic Electricity building-up process.
Lead dioxide electrode has the satisfactory electrical conductivity of metalloid, in water solution system, have preferably electrocatalysis characteristic, overpotential for oxygen evolution high, can pass through large electric current and good corrosion resistance, in electrochemical industry, obtain to use as insoluble anode very early.At first, do not have matrix in the lead dioxide electrode, have the mechanical workout difficulty, yield rate is low, and is fragile, manufacturing time length and high in cost of production problem.In order to improve the performance of lead dioxide electrode, the metal titanium that people use that corrosion resistance is strong, thermal expansivity and plumbic oxide are approaching utilizes electro-deposition techniques to prepare ti-supported lead dioxide electric pole Ti/PbO thereon as matrix 2This electrode not only quality is light, and the difficult deposition layer that causes because of temperature variation that produces is peeled off problem.Titanium is owing to having stronger erosion resistance, its thermal expansivity and PbO 2Approach, so be difficult for like this deposition layer peeling that generation causes because of temperature variation by widely as PbO 2The matrix of electrode.Experts and scholars both domestic and external have carried out a large amount of research to this, this work constantly deeply development just in the ascendant.
Present PbO 2Although oneself obtains some progress the research of electrode, but many places are in laboratory study or small-scale application stage, be still waiting at aspects such as stability, electro catalytic activities to improve, the problem of existence is in particular in the following aspects: the surfactivity layer is combined the firm not β-PbO as the electrode activity layer with substrate 2Be a kind of porous material, and internal stress is larger, the crack easily appears in coating, and in the electrode use procedure, electrolytic solution may expand and is seeped into substrate surface and causes active coating to come off.
PbO 2Dissolving PbO 2Electrode uses the rear surface thickly dotted hole can occur, and corner angle disappear, and is that the decline that this not only can cause electrode electrocatalysis characteristic and stability also might cause Lead contamination due to the PbO2 dissolving.
For the stability, electroconductibility and the erosion resistance that improve lead dioxide electrode, the researchist has developed the novel lead dioxide electrode that is made of titanium matrix, bottom, middle layer and upper layer.Bottom can silver-plated, pb-ag alloy, or coating palladous oxide, tin-antimony oxide etc.; The middle layer is not for existing the α-PbO of distortion 2Coating; Upper layer is β-PbO 2α-PbO 2Layer plays the transitional function that buffering merges, and prevents β-PbO 2Peeling off of layer.
Titanium base PbO 2When electrode has good electroconductibility and degradation capability, also there are some problems, i.e. the crystal boundary slit of coating, the O that produces during electrolysis 2Form the TiO of poorly conductive through the crystal boundary slit titanium oxide matrix of coating 2Cause the matrix passivation, worsen electrode performance.
In order to overcome this passivation phenomenon, developed and on the titanium base, covered first layer of metal or metal oxide as the preparation method in bottom or middle layer.Oxide compound, Au and Al, Ag alloy and Sn that the metal that uses or metal oxide comprise Pt and Pd, the oxide compound of Sb, early stage main on the titanium matrix compound platinum metals and coating platinum group metal oxide make the bottom of electrode, thereby avoid the anti-TiO in Gaoyang 2Formation.
Preparation method and application's condition of research and discussion electrode materials makes electrode have specific composition, structure, is the problem that merits attention thereby have satisfactory stability, the work-ing life of growing and good electro catalytic activity and reaction preference.The anode material that development is used in sulfuric acid medium carries out deep fundamental research to the factor that affects anode material preparation process, structure and use properties and seems and be even more important.Adopt rare earth oxide (Pr 2O 3) improve Ti base PbO 2The catalytic performance of electrode and chemical property are fundamentally to solve present Ti/PbO 2The problems such as electrode inactivation, the electrocatalysis characteristic that metal oxide electrode exists is poor are the most promising research directions.
Summary of the invention
The present invention relates to a kind of rare earth oxide-praseodymium sesquioxide (Pr for preparing 2O 3) the high catalytic activity Ti base nanometer PbO of modification 2Modified electrode material preparation method, one of related key issue are preparation rare earth praseodymium sesquioxide (Pr 2O 3) modification the lead electrode material.The present invention adopts electrodip process, selects rare earth oxide-praseodymium sesquioxide 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 the rare earth praseodymium nitrate, adopt the cyclic voltammetric electrochemical plating to Ti/PbO 2Electrode carries out modification, obtains praseodymium sesquioxide (Pr 2O 3) the high catalytic activity Ti/PbO of doping vario-property 2-Pr 2O 3The modified electrode material.
Convenient and swift method prepares rare earth oxide-praseodymium sesquioxide (Pr 2O 3) 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 3-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 praseodymium nitrate, adopt the cyclic voltammetric electrochemical plating to Ti/PbO 2Electrode carries out modification, obtains praseodymium sesquioxide (Pr 2O 3) the high catalytic activity Ti/PbO of doping vario-property 2-Pr 2O 3The modified electrode material
Wherein: described in the alkaline electro plating bath, first by high current density, by low current density, obtain first transition layer α-PbO2 layer afterwards, 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 praseodymium nitrate, praseodymium nitrate content are praseodymium nitrate 0.2～0.5mol/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 0.02～0.1Vs-1, the scanning number of turns 40～80.
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 0.2mol/l praseodymium nitrate, adopting the cyclic voltammetry sweep limit is 0～2V, and scanning speed is 0.02Vs -1Electrode is carried out rare-earth-doped modification, and scanning 40 circles namely obtain Ti/Pr 2O 3-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 0.2mol/l praseodymium nitrate, adopting the cyclic voltammetry sweep limit is 0～2V, and scanning speed is 0.04Vs -1Electrode is carried out rare-earth-doped modification, and scanning 40 circles namely obtain Ti/Pr 2O 3-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/3-PbO that the 3rd step was made 2Be placed on the solution of 0.3mol/l praseodymium nitrate, adopting the cyclic voltammetry sweep limit is 0～2V, and scanning speed is 0.06Vs -1Electrode is carried out rare-earth-doped modification, and scanning 40 circles namely obtain Ti/Pr 2O 3-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 0.4mol/l praseodymium nitrate, adopting the cyclic voltammetry sweep limit is 0～2V, and scanning speed is 0.08Vs -1Electrode is carried out rare-earth-doped modification, and scanning 80 circles namely obtain Ti/Pr 2O 3-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-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 2.5V, electroplates 2h.
4, the Ti/ β-PbO that the 3rd step was made 2Be placed on the solution of 0.5mol/l praseodymium nitrate, adopting the cyclic voltammetry sweep limit is 0～2V, and scanning speed is 0.1Vs -1Electrode is carried out rare upper doping vario-property, and scanning 60 circles namely obtain Ti/Pr 2O 3-PbO 2

Claims (6)

1. one kind prepares rare earth oxide-praseodymium sesquioxide (Pr 2O 3) 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 praseodymium 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 Praseodymium trioxide (Pr 2O 3) the high catalytic activity Ti/PbO of doping vario-property 2-Pr 2O 3The 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 0.1～0.4mo1L -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 0.65molL -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 upper praseodymium nitrate is praseodymium nitrate 0.2～0.5molL -1
6. in the method for claim 1, cyclic voltammetry scanning scans the number of turns 40～80.
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CN103205780A (en) * 2013-04-15 2013-07-17 昆明理工恒达科技有限公司 Grate type titanium-based PbO2 electrode for nonferrous metal electrodeposition and preparation method of grate type titanium-based PbO2 electrode
CN110707369A (en) * 2019-09-27 2020-01-17 天能电池集团股份有限公司 Preparation method of long-life storage battery and storage battery
CN113716654A (en) * 2021-09-01 2021-11-30 安徽康菲尔检测科技有限公司 Preparation method of high-conductivity alloy catalytic electrode and prepared electrode

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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
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CN103205780A (en) * 2013-04-15 2013-07-17 昆明理工恒达科技有限公司 Grate type titanium-based PbO2 electrode for nonferrous metal electrodeposition and preparation method of grate type titanium-based PbO2 electrode
CN110707369A (en) * 2019-09-27 2020-01-17 天能电池集团股份有限公司 Preparation method of long-life storage battery and storage battery
CN110707369B (en) * 2019-09-27 2021-04-13 天能电池集团股份有限公司 Preparation method of long-life storage battery and storage battery
CN113716654A (en) * 2021-09-01 2021-11-30 安徽康菲尔检测科技有限公司 Preparation method of high-conductivity alloy catalytic electrode and prepared electrode
CN113716654B (en) * 2021-09-01 2023-12-26 安徽康菲尔检测科技有限公司 Preparation method of high-conductivity alloy catalytic electrode and prepared electrode

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