CN108823593B - Preparation method of rare earth oxide doped membrane electrode - Google Patents
Preparation method of rare earth oxide doped membrane electrode Download PDFInfo
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- CN108823593B CN108823593B CN201810532969.1A CN201810532969A CN108823593B CN 108823593 B CN108823593 B CN 108823593B CN 201810532969 A CN201810532969 A CN 201810532969A CN 108823593 B CN108823593 B CN 108823593B
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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
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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
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/02—Electrodes; Manufacture thereof not otherwise provided for characterised by shape or form
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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
- 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
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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
- 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 invention provides a preparation method of a rare earth oxide doped membrane electrode, which comprises the following steps: (1) activating a base film; (2) impregnating, adding Pb (NO)3)2、Ce(NO3)2Preparing impregnation liquid, flatly placing the activated SPE membrane, immersing one half of the activated SPE membrane into the impregnation liquid to obtain an impregnated SPE membrane, (3) oxidizing to prepare NaOH or KOH solution, putting the impregnated SPE membrane into the solution, adding an oxidant to obtain β -PbO deposit2、CeO2The obtained SPE membrane is tightly contacted with the catalyst, the catalyst particles are fine, and a better catalytic effect can be obtained, so that the generation efficiency of ozone is improved.
Description
Technical Field
The invention relates to a preparation method of a rare earth oxide doped membrane electrode, in particular to a method for preparing a rare earth oxide doped lead dioxide composite membrane electrode by using a dipping-oxidation method.
Background
The electrolytic method for preparing ozone has the advantages of high concentration of generated ozone and no generation of nitrogen oxides, and is the preferred method for preparing ozone at present. A key component of the electrolytic method is the preparation of the composite membrane electrode, the existing preparation method comprises a hot pressing method and an electrochemical deposition method, but catalyst particles which cannot be obtained by the hot pressing method are large, the activity is low, and the electrochemical deposition method is greatly influenced by electroplating.
Disclosure of Invention
Compared with the prior art, the method for preparing the rare earth oxide-doped lead dioxide composite membrane electrode by the impregnation-oxidation method has the advantages that the membrane is tightly contacted with the catalyst, the catalyst particles are fine, a better catalytic effect can be obtained, and the ozone generation efficiency is improved.
The technical scheme of the invention is as follows:
a preparation method of a rare earth oxide doped membrane electrode comprises the following steps:
(1) activation of base film
Soaking the SPE membrane in absolute ethyl alcohol, performing ultrasonic treatment for 1-60min under certain power, drying in an oven for 1-30min after ultrasonic treatment, soaking the dried SPE membrane in hydrochloric acid or sulfuric acid for 1-10h, washing with deionized water for 1-3 times after soaking, then placing in hydrogen peroxide, and soaking for 0.5-4h to obtain an activated SPE membrane;
(2) impregnation
Mixing 0.1-1mol/LPb(NO3)20.01-0.2mol/L of Ce (NO)3)2Preparing a steeping liquor, flatly placing the activated SPE membrane, immersing one half of the activated SPE membrane into the steeping liquor for 1-10 hours, and washing with deionized water after steeping is finished to obtain the steeped SPE membrane;
(3) oxidation by oxygen
Preparing 1-6mol/L NaOH or KOH solution, putting the soaked SPE membrane into the solution, adding an oxidant, and oxidizing for 1-5h to obtain β -PbO deposit2、CeO2The SPE membrane of (1).
The SPE membrane is selected from the group of Nafion series membranes, preferably Nafion 324.
The ultrasonic power is 10-60W, and the ultrasonic time is preferably 10-30 min.
The concentration of the hydrochloric acid or the sulfuric acid is 0.2-1 mol/L.
The Pb (NO)3)2The concentration is preferably 0.2 to 0.8mol/L, more preferably 0.3 to 0.5mol/L, Ce (NO)3)2The concentration is preferably 0.02 to 0.1mol/L, more preferably 0.03 to 0.06 mol/L.
The impregnation solution also contains 1-100mmol/L NaF, preferably 10-50 mmol/L.
The membrane electrode obtained by the dipping-oxidation method has the advantages that the membrane is tightly contacted with the catalyst, the catalyst particles are fine, and a better catalytic effect can be obtained, so that the ozone generation efficiency is improved. And the rare earth metal is added into the PbO, has a special 4f electronic structure, is extremely easy to deform and can easily enter the PbO in a gap filling or replacement mode2Inside the crystal lattice, so that PbO2The grain refinement of the deposition is reduced, and the microstructure and the catalytic effect of the electrode are improved.
However, rare earth metals are added, and the rare earth metals are easy to deform, so that the ion replacement of the SPE membrane in the dipping process is fast, and the content of lead oxide in the obtained SPE membrane is too low.
Detailed Description
The present invention will be described in detail with reference to specific examples.
Example 1:
a preparation method of a rare earth oxide doped membrane electrode comprises the following steps:
(1) activation of base film
Soaking the SPE membrane in absolute ethyl alcohol, performing ultrasonic treatment for 10min under certain power, drying in an oven for 5min after ultrasonic treatment, soaking the dried SPE membrane in hydrochloric acid or sulfuric acid for 2h, washing with deionized water for 2 times after soaking, then soaking in hydrogen peroxide for 1h to obtain an activated SPE membrane;
(2) impregnation
Adding 0.5mol/L of Pb (NO)3)20.06mol/L of Ce (NO)3)2Preparing a dipping solution with 32mmol/L NaF, flatly placing the activated SPE membrane, dipping half of the activated SPE membrane into the dipping solution for 2 hours, and washing with deionized water after dipping is finished to obtain a dipped SPE membrane;
(3) oxidation by oxygen
Preparing 4.0mol/L NaOH solution, putting the soaked SPE membrane into the solution, adding an oxidant, and oxidizing for 2 hours to obtain β -PbO deposit2、CeO2The SPE membrane of (1).
Tested, β -PbO2、CeO2Respectively in an amount of 75.50mg/cm2And 9.21mg/cm2The oxygen evolution overpotential of the electrode is 2706mV, and the current density is 30mA/cm2The current efficiency was 28.2%, and the accelerated lifetime was 2.16 hours (actual lifetime was about 224 days).
Example 2:
a preparation method of a rare earth oxide doped membrane electrode comprises the following steps:
(1) activation of base film
Soaking the SPE membrane in absolute ethyl alcohol, performing ultrasonic treatment for 10min under certain power, drying in an oven for 5min after ultrasonic treatment, soaking the dried SPE membrane in hydrochloric acid or sulfuric acid for 2h, washing with deionized water for 2 times after soaking, then soaking in hydrogen peroxide for 1h to obtain an activated SPE membrane;
(2) impregnation
Adding 0.5mol/L of Pb (NO)3)20.06mol/L of Ce (NO)3)2Preparing a dipping solution with 10mmol/L NaF, flatly placing the activated SPE membrane, dipping half of the activated SPE membrane into the dipping solution for 2 hours, and washing with deionized water after dipping is finished to obtain a dipped SPE membrane;
(3) oxidation by oxygen
Preparing 4.0mol/L NaOH solution, putting the soaked SPE membrane into the solution, adding an oxidant, and oxidizing for 2 hours to obtain β -PbO deposit2、CeO2The SPE membrane of (1).
Tested, β -PbO2、CeO2Respectively in an amount of 66.81mg/cm2And 11.20mg/cm2The oxygen evolution overpotential of the electrode is 2816mV, and the current density is 30mA/cm2The current efficiency was 26.6% and the accelerated lifetime was 2.20 hours (actual lifetime was about 228 days).
Example 3:
a preparation method of a rare earth oxide doped membrane electrode comprises the following steps:
(1) activation of base film
Soaking the SPE membrane in absolute ethyl alcohol, performing ultrasonic treatment for 10min under certain power, drying in an oven for 5min after ultrasonic treatment, soaking the dried SPE membrane in hydrochloric acid or sulfuric acid for 2h, washing with deionized water for 2 times after soaking, then soaking in hydrogen peroxide for 1h to obtain an activated SPE membrane;
(2) impregnation
Adding 0.5mol/L of Pb (NO)3)20.06mol/L of Ce (NO)3)2Preparing a dipping solution with 100mmol/L NaF, flatly placing the activated SPE membrane, dipping half of the activated SPE membrane into the dipping solution for 2 hours, and washing with deionized water after dipping is finished to obtain a dipped SPE membrane;
(3) oxidation by oxygen
Preparing 4.0mol/L NaOH solution, putting the soaked SPE membrane into the solutionAdding an oxidant, and oxidizing for 2 hours to obtain β -PbO deposit2、CeO2The SPE membrane of (1).
Tested, β -PbO2、CeO2Respectively in an amount of 62.05mg/cm2And 5.54mg/cm2The oxygen evolution overpotential of the electrode is 2685mV, and the current density is 30mA/cm2The current efficiency was 25.6% and the accelerated lifetime was 2.19 hours (actual lifetime was about 228 days).
Comparative example 1:
a preparation method of a rare earth oxide doped membrane electrode comprises the following steps:
(1) activation of base film
Soaking the SPE membrane in absolute ethyl alcohol, performing ultrasonic treatment for 10min under certain power, drying in an oven for 5min after ultrasonic treatment, soaking the dried SPE membrane in hydrochloric acid or sulfuric acid for 2h, washing with deionized water for 2 times after soaking, then soaking in hydrogen peroxide for 1h to obtain an activated SPE membrane;
(2) impregnation
Adding 0.5mol/L of Pb (NO)3)20.06mol/L of Ce (NO)3)2Preparing a steeping liquor, flatly placing the activated SPE membrane, immersing one half of the activated SPE membrane into the steeping liquor for 2 hours, and washing the SPE membrane with deionized water after the steeping is finished to obtain the steeped SPE membrane;
(3) oxidation by oxygen
Preparing 4.0mol/L NaOH solution, putting the soaked SPE membrane into the solution, adding an oxidant, and oxidizing for 2 hours to obtain β -PbO deposit2、CeO2The SPE membrane of (1).
Tested, β -PbO2、CeO2Respectively in an amount of 48.08mg/cm2And 16.20mg/cm2The oxygen evolution overpotential of the electrode is 2903mV, and the current density is 30mA/cm2The current efficiency was 23.2%, and the accelerated lifetime was 1.89 hours (actual lifetime was about 197 days).
As can be seen from comparison between example 1 and comparative example 1, when NaF is not added, the substitution amount of Ce is large, the amount of Pb is small, and a large amount of Pb is wasted, and the cost of Ce is high, and the combination of the two is not reasonable, so that the current efficiency is also low. It can be seen from the comparison of examples 1 to 3 that the NaF content has a large influence on the replacement rate of Pb and Ce because F can also form a complex with Pb, and the NaF content is too high, so that the replacement rate of Pb is influenced, but too low, the replacement rates of Pb and Ce cannot be well balanced, and the existence of F also contributes to the improvement of the service life of the electrode, thereby further reducing the cost of the membrane electrode.
Claims (7)
1. A preparation method of a rare earth oxide doped membrane electrode is characterized by comprising the following steps:
(1) activation of base film
Soaking the SPE membrane in absolute ethyl alcohol, performing ultrasonic treatment for 1-60min under certain power, drying in an oven for 1-30min after ultrasonic treatment, soaking the dried SPE membrane in hydrochloric acid or sulfuric acid for 1-10h, washing with deionized water for 1-3 times after soaking, then placing in hydrogen peroxide, and soaking for 0.5-4h to obtain an activated SPE membrane;
the SPE membrane is Nafion 324;
(2) impregnation
Adding 0.1-1mol/L of Pb (NO)3)20.01-0.2mol/L of Ce (NO)3)2Preparing a steeping liquor, flatly placing the activated SPE membrane, immersing one half of the activated SPE membrane into the steeping liquor for 1-10 hours, and washing with deionized water after steeping is finished to obtain the steeped SPE membrane;
the impregnation liquid also comprises 10-32mmol/L NaF;
(3) oxidation by oxygen
Preparing 1-6mol/L NaOH or KOH solution, putting the soaked SPE membrane into the solution, adding an oxidant, and oxidizing for 1-5h to obtain β -PbO deposit2、CeO2The SPE membrane of (1).
2. The method of claim 1, wherein the ultrasonic power is 10-60W and the ultrasonic time is 10-30 min.
3. The method according to claim 1, wherein the concentration of the hydrochloric acid or sulfuric acid is 0.2 to 1 mol/L.
4. The method according to claim 1, wherein the Pb (NO)3)2The concentration is 0.2-0.8 mol/L.
5. The method according to claim 1, wherein the Pb (NO)3)2The concentration is 0.3-0.5 mol/L.
6. The method according to claim 1, wherein Ce (NO)3)2The concentration is 0.02-0.1 mol/L.
7. The method according to claim 1, wherein Ce (NO)3)2The concentration is 0.03-0.06 mol/L.
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Citations (4)
| 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 |
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- 2018-05-30 CN CN201810532969.1A patent/CN108823593B/en active Active
Patent Citations (4)
| 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)
| Title |
|---|
| PbO2/SPE复合膜电极的制备与优化;周雅宁;《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》;20061115;第B014-216页 * |
| 浸渍-氧化法制备β-PbO2-SPE复合膜电极的研究;万亚珍;《中国博士学位论文全文数据库 工程科技Ⅰ辑》;20071115;第B014-83页 * |
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