CN108823593A - A kind of preparation method of the membrane electrode of rare earth doped oxide - Google Patents

A kind of preparation method of the membrane electrode of rare earth doped oxide Download PDF

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CN108823593A
CN108823593A CN201810532969.1A CN201810532969A CN108823593A CN 108823593 A CN108823593 A CN 108823593A CN 201810532969 A CN201810532969 A CN 201810532969A CN 108823593 A CN108823593 A CN 108823593A
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spe film
film
dipping
spe
maceration extract
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CN108823593B (en
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樊国荣
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Central Oxygen Technology (guangzhou) Co Ltd
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Central Oxygen Technology (guangzhou) Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B1/00—Electrolytic production of inorganic compounds or non-metals
    • C25B1/01—Products
    • C25B1/13—Ozone
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
    • C25B11/02—Electrodes; Manufacture thereof not otherwise provided for characterised by shape or form
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
    • C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
    • C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
    • C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
    • C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
    • C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
    • C25B11/091—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of at least one catalytic element and at least one catalytic compound; consisting of two or more catalytic elements or catalytic compounds

Abstract

The present invention provides a kind of preparation methods of the membrane electrode of rare earth doped oxide, include the following steps：（1）Basement membrane activation；（2）Dipping, by Pb (NO3)2、Ce(NO3)2It is configured to maceration extract, the SPE film of activation is laid flat, its half is immersed in maceration extract, the SPE film after being impregnated；（3）NaOH or KOH solution are prepared in oxidation, by the SPE film merging solution after dipping, oxidant are added, obtains being deposited with β-PbO2、CeO2SPE film, contact of the obtained film with catalyst is close, and catalyst granules is fine and closely woven, available better catalytic effect, so that the formation efficiency of ozone is improved.

Description

A kind of preparation method of the membrane electrode of rare earth doped oxide
Technical field
The present invention relates to a kind of preparation method of the membrane electrode of rare earth doped oxide, specific is to use dipping-oxidation The method of the brown lead oxide compound film electrode of the rare earth doped oxide of method preparation.
Background technique
Electrolysis method, which prepares ozone, to be had the advantages that produce ozoniferous concentration height, does not generate nitrogen oxides, smelly to prepare at present The method of oxygen first choice.And a critical component of electrolysis method is the preparation of compound film electrode, existing preparation method includes hot pressing Method and electrochemical deposition method, but the catalyst granules that pressure sintering is unable to get is larger, and activity is lower, and electrochemical deposition method is electroplated It is affected.
Summary of the invention
In order to solve the problem above-mentioned, the invention proposes a kind of dipping-oxidizing process to prepare the two of rare earth doped oxide The method of lead oxide compound film electrode, compared to the prior art, contact of the film with catalyst is close, and catalyst granules is fine and closely woven, can To obtain better catalytic effect, so that the formation efficiency of ozone is improved.
Technical scheme is as follows：
A kind of preparation method of the membrane electrode of rare earth doped oxide, includes the following steps：
（1）Basement membrane activation
SPE film is soaked in dehydrated alcohol, ultrasound 1-60min under certain power, ultrasound is placed in baking oven dry 1- Dry SPE film is placed in hydrochloric acid or sulfuric acid by 30min, is impregnated 1-10h, is cleaned 1-3 times after immersion with deionized water, then It is placed in hydrogen peroxide, impregnates 0.5-4h, the SPE film activated；
（2）Dipping
By the Pb (NO of 0.1-1mol/L3)2, 0.01-0.2mol/L Ce (NO3)2It is configured to maceration extract, the SPE film of activation is flat It puts, its half is immersed in maceration extract, dip time 1-10h, after the completion of dipping, is washed with deionized, after obtaining dipping SPE film；
（3）Oxidation
The NaOH or KOH solution for preparing 1-6mol/L are added in the SPE film merging solution after dipping oxidant, aoxidize 1- 5h obtains being deposited with β-PbO2、CeO2SPE film.
The SPE film is selected from Nafion series membranes, preferably Nafion 324.
The ultrasonic power is 10-60W, the preferred 10-30min of ultrasonic time.
The concentration of the hydrochloric acid or sulfuric acid is 0.2-1mol/L.
Pb (the NO3)2Concentration preferred 0.2-0.8mol/L, more preferable 0.3-0.5mol/L, Ce (NO3)2Concentration is preferred 0.02-0.1mol/L's, more preferable 0.03-0.06mol/L.
The maceration extract also includes the NaF of 1-100mmol/L, preferably 10-50mmol/L.
The membrane electrode obtained by above-mentioned dipping-oxidizing process, contact of the film with catalyst is close, and catalyst granules is fine and closely woven, Available better catalytic effect, so that the formation efficiency of ozone is improved.And it wherein joined rare earth metal, With special 4f electronic structure, and easily deformation, it is easy to enter PbO in a manner of calking or displacement2Intracell, so that PbO2The crystal grain refinement of deposition becomes smaller, and improves the microstructure and catalytic effect of electrode.
But certain problem is also brought when rare earth metal is added, due to its easily deformation, so that in dipping process The ion exchange for neutralizing SPE film is very fast, and oxidation lead content is very few in the SPE film caused, however, by the continuous of inventor Effort is found surprisingly that a certain amount of NaF solution is added in maceration extract solves the problems, such as this, and is determined through experimentation NaF Optimal content, may be in reason Ce and F complexing power it is stronger, to control the replacing velocity of Ce so that Ce and Pb into Enter the balance that SPE film reaches certain, obtains desired SPE compound film electrode.
Specific embodiment
Below in conjunction with specific embodiment, the present invention is described in detail.
Embodiment 1：
A kind of preparation method of the membrane electrode of rare earth doped oxide, includes the following steps：
（1）Basement membrane activation
SPE film is soaked in dehydrated alcohol, ultrasound 10min under certain power, ultrasound is placed in baking oven dry 5min, will do Dry SPE film is placed in hydrochloric acid or sulfuric acid, is impregnated 2h, is cleaned 2 times, be subsequently placed in hydrogen peroxide with deionized water after immersion, is soaked Steep 1h, the SPE film activated；
（2）Dipping
By the Pb (NO of 0.5mol/L3)2, 0.06mol/L Ce (NO3)2It is configured to maceration extract with the NaF of 32mmol/L, activation SPE film is laid flat, its half is immersed in maceration extract, dip time 2h, after the completion of dipping, is washed with deionized, is soaked SPE film after stain；
（3）Oxidation
The NaOH solution for preparing 4.0mol/L is added in the SPE film merging solution after dipping oxidant, aoxidizes 2h, sunk Product has β-PbO2、CeO2SPE film.
After tested, β-PbO2、CeO2Content be respectively 75.50mg/cm2And 9.21mg/cm2, the overpotential for oxygen evolution of electrode For 2706mV, current density 30mA/cm2Under current efficiency be 28.2%, accelerated service life be 2.16 hours（Actual use Service life about 224 days）.
Embodiment 2：
A kind of preparation method of the membrane electrode of rare earth doped oxide, includes the following steps：
（1）Basement membrane activation
SPE film is soaked in dehydrated alcohol, ultrasound 10min under certain power, ultrasound is placed in baking oven dry 5min, will do Dry SPE film is placed in hydrochloric acid or sulfuric acid, is impregnated 2h, is cleaned 2 times, be subsequently placed in hydrogen peroxide with deionized water after immersion, is soaked Steep 1h, the SPE film activated；
（2）Dipping
By the Pb (NO of 0.5mol/L3)2, 0.06mol/L Ce (NO3)2It is configured to maceration extract with the NaF of 10mmol/L, activation SPE film is laid flat, its half is immersed in maceration extract, dip time 2h, after the completion of dipping, is washed with deionized, is soaked SPE film after stain；
（3）Oxidation
The NaOH solution for preparing 4.0mol/L is added in the SPE film merging solution after dipping oxidant, aoxidizes 2h, sunk Product has β-PbO2、CeO2SPE film.
After tested, β-PbO2、CeO2Content be respectively 66.81mg/cm2And 11.20mg/cm2, the analysis oxygen of electrode is excessively electric Position is 2816mV, current density 30mA/cm2Under current efficiency be 26.6%, accelerated service life be 2.20 hours（Actually make With the service life about 228 days）.
Embodiment 3：
A kind of preparation method of the membrane electrode of rare earth doped oxide, includes the following steps：
（1）Basement membrane activation
SPE film is soaked in dehydrated alcohol, ultrasound 10min under certain power, ultrasound is placed in baking oven dry 5min, will do Dry SPE film is placed in hydrochloric acid or sulfuric acid, is impregnated 2h, is cleaned 2 times, be subsequently placed in hydrogen peroxide with deionized water after immersion, is soaked Steep 1h, the SPE film activated；
（2）Dipping
By the Pb (NO of 0.5mol/L3)2, 0.06mol/L Ce (NO3)2It is configured to maceration extract with the NaF of 100mmol/L, is activated SPE film lay flat, its half is immersed in maceration extract, dip time 2h, after the completion of dipping, is washed with deionized, obtains SPE film after dipping；
（3）Oxidation
The NaOH solution for preparing 4.0mol/L is added in the SPE film merging solution after dipping oxidant, aoxidizes 2h, sunk Product has β-PbO2、CeO2SPE film.
After tested, β-PbO2、CeO2Content be respectively 62.05mg/cm2And 5.54mg/cm2, the overpotential for oxygen evolution of electrode For 2685mV, current density 30mA/cm2Under current efficiency be 25.6%, accelerated service life be 2.19 hours（Actual use Service life about 228 days）.
Comparative example 1：
A kind of preparation method of the membrane electrode of rare earth doped oxide, includes the following steps：
（1）Basement membrane activation
SPE film is soaked in dehydrated alcohol, ultrasound 10min under certain power, ultrasound is placed in baking oven dry 5min, will do Dry SPE film is placed in hydrochloric acid or sulfuric acid, is impregnated 2h, is cleaned 2 times, be subsequently placed in hydrogen peroxide with deionized water after immersion, is soaked Steep 1h, the SPE film activated；
（2）Dipping
By the Pb (NO of 0.5mol/L3)2, 0.06mol/L Ce (NO3)2It is configured to maceration extract, the SPE film of activation is laid flat, by it Half immerses in maceration extract, dip time 2h, after the completion of dipping, is washed with deionized, the SPE film after being impregnated；
（3）Oxidation
The NaOH solution for preparing 4.0mol/L is added in the SPE film merging solution after dipping oxidant, aoxidizes 2h, sunk Product has β-PbO2、CeO2SPE film.
After tested, β-PbO2、CeO2Content be respectively 48.08mg/cm2And 16.20mg/cm2, the analysis oxygen of electrode is excessively electric Position is 2903mV, current density 30mA/cm2Under current efficiency be 23.2%, accelerated service life be 1.89 hours（Actually make With the service life about 197 days）.
Can be seen that from the comparison of embodiment 1 and comparative example 1 when not adding NaF, the replacement amount of Ce is larger, the amount of Pb compared with It is few, cause a large amount of Pb to be wasted, and the higher cost of Ce, the two collocation is unreasonable, so that current efficiency is also low.From implementation The comparison of example 1-3 can be seen that NaF content and be affected to Pb, Ce replacing velocity, because F can also form complex compound with Pb, NaF content is excessive, and the displacement of Pb is caused to receive influence, but it is very few when cannot balance the replacing velocity of Pb and Ce, while F well Presence also contribute to the improvement of electrode life, to further decrease the cost of membrane electrode.

Claims (7)

1. a kind of preparation method of the membrane electrode of rare earth doped oxide, which is characterized in that include the following steps：
（1）Basement membrane activation
SPE film is soaked in dehydrated alcohol, ultrasound 1-60min under certain power, ultrasound is placed in baking oven dry 1- Dry SPE film is placed in hydrochloric acid or sulfuric acid by 30min, is impregnated 1-10h, is cleaned 1-3 times after immersion with deionized water, then It is placed in hydrogen peroxide, impregnates 0.5-4h, the SPE film activated；
（2）Dipping
By the Pb (NO of 0.1-1mol/L3)2, 0.01-0.2mol/L Ce (NO3)2It is configured to maceration extract, the SPE film of activation is laid flat, Its half is immersed in maceration extract, dip time 1-10h, after the completion of dipping, is washed with deionized, after being impregnated SPE film；
（3）Oxidation
The NaOH or KOH solution for preparing 1-6mol/L are added in the SPE film merging solution after dipping oxidant, aoxidize 1- 5h obtains being deposited with β-PbO2、CeO2SPE film.
2. the method according to claim 1, wherein the SPE film is selected from Nafion series membranes, preferably Nafion 324。
3. the method according to claim 1, wherein the ultrasonic power is 10-60W, the preferred 10- of ultrasonic time 30min。
4. the method according to claim 1, wherein the concentration of the hydrochloric acid or sulfuric acid is 0.2-1mol/L.
5. the method according to claim 1, wherein the Pb (NO3)2Concentration preferred 0.2-0.8mol/L, it is more excellent Select 0.3-0.5mol/L.
6. the method according to claim 1, wherein Ce (NO3)2The preferred 0.02-0.1mol/L's of concentration, it is more excellent Select 0.03-0.06mol/L.
7. according to the method described in claim 1, the maceration extract also includes the NaF of 1-100mmol/L, preferably 10-50mmol/ L。
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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1683596A (en) * 2004-04-15 2005-10-19 石油大学(北京) Method for producing hydrogen and storaging hydrogen integrately
CN102899683A (en) * 2012-09-17 2013-01-30 淮南师范学院 Preparation method of Ti-based nano-CeO2/PbO2 modified electrode
CN103014800A (en) * 2012-12-29 2013-04-03 北京化工大学 Method for preparing cerium-doped graphite-based lead dioxide catalytic electrode
CN107604379A (en) * 2017-09-25 2018-01-19 浙江高成绿能科技有限公司 A kind of SPE membrane electrodes and its preparation technology

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1683596A (en) * 2004-04-15 2005-10-19 石油大学(北京) Method for producing hydrogen and storaging hydrogen integrately
CN102899683A (en) * 2012-09-17 2013-01-30 淮南师范学院 Preparation method of Ti-based nano-CeO2/PbO2 modified electrode
CN103014800A (en) * 2012-12-29 2013-04-03 北京化工大学 Method for preparing cerium-doped graphite-based lead dioxide catalytic electrode
CN107604379A (en) * 2017-09-25 2018-01-19 浙江高成绿能科技有限公司 A kind of SPE membrane electrodes and its preparation technology

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
万亚珍: "浸渍-氧化法制备β-PbO2-SPE复合膜电极的研究", 《中国博士学位论文全文数据库 工程科技Ⅰ辑》 *
周雅宁: "PbO2/SPE复合膜电极的制备与优化", 《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》 *

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