CN108914151B - Preparation method of rare earth oxide and graphene doped membrane electrode - Google Patents
Preparation method of rare earth oxide and graphene doped membrane electrode Download PDFInfo
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- CN108914151B CN108914151B CN201810532968.7A CN201810532968A CN108914151B CN 108914151 B CN108914151 B CN 108914151B CN 201810532968 A CN201810532968 A CN 201810532968A CN 108914151 B CN108914151 B CN 108914151B
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Abstract
The invention provides a preparation method of a membrane electrode doped with rare earth oxide and graphene, comprisingThe method comprises the following steps: a preparation method of a rare earth oxide and graphene doped membrane electrode is characterized by comprising the following steps: (1) doping graphene, dissolving perfluorinated sulfonic acid ion exchange resin into an organic solution to prepare a graphene dispersion solution, adding the dispersion solution into a resin solution, and performing ultrasonic dispersion uniformly; (2) preparing a membrane; (3) impregnating, adding Pb (NO)3)2、Ce(NO3)2Preparing a composite membrane with NaF, preparing a dipping solution with NaF, dipping the composite membrane to obtain a dipped composite membrane, (4) oxidizing, preparing a NaOH or KOH solution, putting the dipped composite membrane into the solution, adding an oxidant to obtain β -PbO deposit2、CeO2The composite membrane of (3). The obtained membrane is closely 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 and graphene doped membrane electrode, in particular to a method for preparing a rare earth oxide and graphene 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
In order to solve the problems, the invention provides a method for preparing a rare earth oxide and graphene doped lead dioxide composite membrane electrode by using a dipping-oxidation method, compared with the prior art, the membrane is tightly contacted with a catalyst, the catalyst particles are fine, and a better catalytic effect can be obtained, so that the generation efficiency of ozone is improved.
The technical scheme of the invention is as follows:
a preparation method of a rare earth oxide and graphene doped membrane electrode comprises the following steps:
(1) doped graphene
Dissolving perfluorosulfonic acid ion exchange resin into an organic solution, dispersing graphene into ethanol, performing ultrasonic treatment for 1-30min under a certain power to form 1-10g/L dispersion liquid, adding the dispersion liquid into the perfluorosulfonic acid ion exchange resin solution, and performing ultrasonic dispersion uniformly;
(2) film production
Taking a tetrafluoroethylene container, placing an SPE membrane on a bottom layer, uniformly pouring the SPE membrane on the SPE membrane, and volatilizing a solvent to form a composite membrane of which the bottom layer is the SPE membrane and the upper layer is an exchange membrane layer containing graphene;
(3) impregnation
Adding 0.1-1mol/L of Pb (NO)3)20.01-0.2mol/L of Ce (NO)3)2Preparing a steeping liquor with 1-100mmol/L NaF, flatly placing the composite membrane obtained in the step (2), immersing an exchange membrane layer containing graphene into the steeping liquor for 1-10h, and washing with deionized water after steeping is finished to obtain the steeped composite membrane;
(4) oxidation by oxygen
Preparing 1-6mol/L NaOH or KOH solution, putting the dipped composite membrane into the solution, adding an oxidant, and oxidizing for 1-5h to obtain β -PbO deposit2、CeO2The composite membrane of (3).
The ultrasonic power in the step (1) is 10-60W, and the ultrasonic time is preferably 2-10 min.
The SPE membrane in step (2) is selected from Nafion series membranes, preferably Nafion 324.
The thickness ratio of the SPE membrane to the exchange membrane layer containing graphene is 10-1:1, preferably 5-2: 1.
In the step (3), 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 NaF is preferably 10 to 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.
The graphene is a two-dimensional honeycomb structure consisting of single-layer carbon atoms, the basic structural unit of the graphene is the most stable six-membered ring structure in an organic material, the graphene has good chemical stability, is a typical representative of a two-dimensional nano material, and the graphene also has excellent electrical property and catalytic property. According to the invention, the solution mixing method is creatively used, so that the graphene is uniformly distributed in the membrane electrode and is cooperated with the lead oxide to catalyze the generation of ozone, and the catalysis efficiency of the electrode is improved.
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 and graphene doped membrane electrode comprises the following steps:
(1) doped graphene
Dissolving perfluorosulfonic acid ion exchange resin into an organic solution, dispersing graphene into ethanol, performing ultrasonic treatment for 10min under the ultrasonic power of 40W to form 8g/L dispersion liquid, adding the dispersion liquid into the perfluorosulfonic acid ion exchange resin solution, and performing uniform ultrasonic dispersion;
(2) film production
Taking a tetrafluoroethylene container, placing an SPE membrane on a bottom layer, uniformly pouring the SPE membrane on the SPE membrane, and volatilizing a solvent to form a composite membrane of which the bottom layer is the SPE membrane and the upper layer is an exchange membrane layer containing graphene;
(3) impregnation
Adding 0.5mol/L of Pb (NO)3)20.06mol/L of Ce (NO)3)2Preparing a steeping liquor with 32mmol/L NaF, flatly placing the composite membrane obtained in the step (2), immersing an exchange membrane layer containing graphene into the steeping liquor for 2 hours, and washing with deionized water after the steeping is finishedWashing to obtain a dipped composite film;
(4) oxidation by oxygen
Preparing 4.0mol/L NaOH solution, putting the dipped composite membrane into the solution, adding an oxidant, and oxidizing for 2 hours to obtain β -PbO deposit2、CeO2The composite membrane of (3).
Tested, β -PbO2、CeO2Respectively in an amount of 73.08mg/cm2And 8.23mg/cm2The oxygen evolution overpotential of the electrode is 2613mV, and the current density is 30mA/cm2The current efficiency was 30.1%, and the accelerated lifetime was 2.40 hours (actual lifetime was about 249 days).
Example 2:
a preparation method of a rare earth oxide and graphene doped membrane electrode comprises the following steps:
(1) doped graphene
Dissolving perfluorosulfonic acid ion exchange resin into an organic solution, dispersing graphene into ethanol, performing ultrasonic treatment for 10min under the ultrasonic power of 40W to form 8g/L dispersion liquid, adding the dispersion liquid into the perfluorosulfonic acid ion exchange resin solution, and performing uniform ultrasonic dispersion;
(2) film production
Taking a tetrafluoroethylene container, placing an SPE membrane on a bottom layer, uniformly pouring the SPE membrane on the SPE membrane, and volatilizing a solvent to form a composite membrane of which the bottom layer is the SPE membrane and the upper layer is an exchange membrane layer containing graphene;
(3) impregnation
Adding 0.5mol/L of Pb (NO)3)20.06mol/L of Ce (NO)3)2Preparing a steeping liquor with 10mmol/L NaF, flatly placing the composite membrane obtained in the step (2), immersing an exchange membrane layer containing graphene into the steeping liquor for 2 hours, and washing with deionized water after the steeping is finished to obtain the steeped composite membrane;
(4) oxidation by oxygen
Preparing 4.0mol/L NaOH solution, putting the dipped composite membrane into the solution, adding an oxidant, and oxidizing for 2 hours to obtain β -PbO deposit2、CeO2The composite membrane of (3).
Tested, β -PbO2、CeO2Respectively in an amount of 60.50mg/cm2And 10.05mg/cm2The oxygen evolution overpotential of the electrode is 2750mV, and the current density is 30mA/cm2The current efficiency was 27.8%, and the accelerated lifetime was 2.17 hours (actual lifetime was about 225 days).
Comparative example 1:
similar to example 1, except that no graphene was added in step (1).
Tested, β -PbO2、CeO2Respectively in an amount of 45.22mg/cm2And 14.69mg/cm2The oxygen evolution overpotential of the electrode is 2855mV, and the current density is 30mA/cm2The current efficiency was 22.2%, and the accelerated lifetime was 2.01 hours (actual lifetime was about 209 days).
As can be seen from comparison between example 1 and comparative example 1, when no graphene is added, the catalytic effect of the electrode is poor, the current efficiency is low, the service life is reduced, and the cost is increased. In the embodiment 1-2, the ion exchange resin is dissolved first, and the graphene is dispersed in a solution state, so that the graphene has a good dispersion effect, the excellent catalytic performance and electrical performance of the graphene are exerted to the greatest extent, and the catalytic performance of the membrane electrode is improved.
Claims (10)
1. A preparation method of a rare earth oxide and graphene doped membrane electrode is characterized by comprising the following steps:
(1) doped graphene
Dissolving perfluorosulfonic acid ion exchange resin into an organic solution, dispersing graphene into ethanol, performing ultrasonic treatment for 1-30min under a certain power to form 1-10g/L dispersion liquid, adding the dispersion liquid into the perfluorosulfonic acid ion exchange resin solution, and performing ultrasonic dispersion uniformly;
wherein the ultrasonic power is 10-60W, and the ultrasonic time is 2-10 min;
(2) film production
Taking a tetrafluoroethylene container, placing an SPE membrane on a bottom layer, uniformly pouring the SPE membrane on the SPE membrane, and volatilizing a solvent to form a composite membrane of which the bottom layer is the SPE membrane and the upper layer is an exchange membrane layer containing graphene;
(3) impregnation
Adding 0.1-1mol/L of Pb (NO)3)20.01-0.2mol/L of Ce (NO)3)2Preparing a steeping liquor with 1-100mmol/L NaF, flatly placing the composite membrane obtained in the step (2), immersing an exchange membrane layer containing graphene into the steeping liquor for 1-10h, and washing with deionized water after steeping is finished to obtain the steeped composite membrane;
(4) oxidation by oxygen
Preparing 1-6mol/L NaOH or KOH solution, putting the dipped composite membrane into the solution, adding an oxidant, and oxidizing for 1-5h to obtain β -PbO deposit2、CeO2The composite membrane of (3).
2. The method as claimed in claim 1, wherein the SPE membrane in step (2) is selected from Nafion series membranes.
3. The method as claimed in claim 1, wherein the SPE membrane in step (2) is selected from Nafion 324.
4. The method as claimed in claim 1, wherein the thickness ratio of the SPE membrane to the graphene containing exchange membrane layer is 10-1: 1.
5. The method as claimed in claim 1, wherein the thickness ratio of the SPE membrane to the graphene containing exchange membrane layer is 5-2: 1.
6. The method according to claim 1, wherein in the step (3), the Pb (NO) is3)2The concentration is 0.2-0.8 mol/L.
7. The method according to claim 1, wherein in the step (3), the Pb (NO) is3)2The concentration is 0.3-0.5 mol/L.
8. According to the claimsThe method according to claim 1, wherein in the step (3), Ce (NO)3)2The concentration is 0.02-0.1 mol/L.
9. The method according to claim 1, wherein in step (3), Ce (NO)3)2The concentration is 0.03-0.06 mol/L.
10. The method according to claim 1, wherein in the step (3), the concentration of NaF is 10-50 mmol/L.
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