CN117199397A - Anti-counter PtIr/C alloy catalyst, and preparation method and application thereof - Google Patents
Anti-counter PtIr/C alloy catalyst, and preparation method and application thereof Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 65
- 229910001339 C alloy Inorganic materials 0.000 title claims abstract description 53
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 81
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 37
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 35
- 229910052741 iridium Inorganic materials 0.000 claims abstract description 30
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 30
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 23
- 239000011259 mixed solution Substances 0.000 claims abstract description 20
- 239000000446 fuel Substances 0.000 claims abstract description 15
- 239000002253 acid Substances 0.000 claims description 64
- 239000000243 solution Substances 0.000 claims description 44
- 239000006185 dispersion Substances 0.000 claims description 39
- 239000000843 powder Substances 0.000 claims description 33
- 239000007787 solid Substances 0.000 claims description 33
- YNJJJJLQPVLIEW-UHFFFAOYSA-M [Ir]Cl Chemical compound [Ir]Cl YNJJJJLQPVLIEW-UHFFFAOYSA-M 0.000 claims description 32
- 239000008367 deionised water Substances 0.000 claims description 31
- 229910021641 deionized water Inorganic materials 0.000 claims description 31
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 31
- 239000007788 liquid Substances 0.000 claims description 29
- 239000002105 nanoparticle Substances 0.000 claims description 25
- 238000006722 reduction reaction Methods 0.000 claims description 21
- 238000001035 drying Methods 0.000 claims description 14
- 238000001914 filtration Methods 0.000 claims description 14
- 238000000227 grinding Methods 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 14
- 238000004140 cleaning Methods 0.000 claims description 13
- 238000001816 cooling Methods 0.000 claims description 13
- 239000000463 material Substances 0.000 claims description 13
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 12
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 12
- 229910021389 graphene Inorganic materials 0.000 claims description 12
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- 239000002041 carbon nanotube Substances 0.000 claims description 8
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 8
- 239000002134 carbon nanofiber Substances 0.000 claims description 7
- 238000006243 chemical reaction Methods 0.000 claims description 7
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical class C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 7
- -1 platinum ions Chemical class 0.000 claims description 6
- 239000012279 sodium borohydride Substances 0.000 claims description 6
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 6
- 239000011148 porous material Substances 0.000 claims description 5
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims description 4
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 4
- 239000008103 glucose Substances 0.000 claims description 4
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 4
- 239000001509 sodium citrate Substances 0.000 claims description 4
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 claims description 4
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims 1
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- 238000010438 heat treatment Methods 0.000 abstract description 7
- 239000002243 precursor Substances 0.000 abstract description 6
- 238000005275 alloying Methods 0.000 abstract description 3
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 abstract description 3
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- 238000001179 sorption measurement Methods 0.000 description 8
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 7
- 238000003917 TEM image Methods 0.000 description 6
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- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
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- 230000002776 aggregation Effects 0.000 description 4
- 229910052786 argon Inorganic materials 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 230000006872 improvement Effects 0.000 description 4
- 238000011065 in-situ storage Methods 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- 239000012528 membrane Substances 0.000 description 4
- 229910021645 metal ion Inorganic materials 0.000 description 4
- 239000007789 gas Substances 0.000 description 3
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- 238000004873 anchoring Methods 0.000 description 2
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Classifications
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
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Abstract
The application relates to a counter electrode PtIr/C alloy catalyst, a preparation method thereof and application thereof to a fuel cell, which are mainly realized by means of co-reduction and heat treatment, wherein the specific preparation method comprises the following steps: 1) Preparing a mixed solution of a platinum precursor and an iridium precursor with a certain concentration; 2) Adding graphitized carbon powder, and stirring and dispersing uniformly; 3) Adding a reducing agent to perform reduction so that Pt and Ir are co-deposited on the carbon carrier; 4) And (3) carrying out high-temperature heat treatment to promote alloying of Pt and Ir, and preparing the PtIr/C alloy catalyst, wherein the PtIr/C alloy catalyst shows excellent anti-counter electrode performance when being applied to a fuel cell.
Description
Technical Field
The application relates to the technical field of nano materials and electrocatalysis, in particular to a counter electrode PtIr/C alloy catalyst, a preparation method thereof and application thereof in fuel cells.
Background
The fuel cell (such as a vehicle-mounted fuel cell and the like) is started and stopped, and the reverse flow of current caused by partial gas deficiency is caused, so that the phenomenon of battery voltage reversal occurs. Under the voltage reversal condition, the carbon carrier is corroded at high potential, the pore structure of the anode catalyst carrier collapses, and Pt nano particles fall off, agglomerate and grow up, so that the effective catalytic activity area of the catalyst is lost, and the output performance of the membrane electrode is seriously affected. The counter electrode is accompanied with the generation of a large amount of heat, which may cause the formation of pinholes on the proton exchange membrane, further reducing the lifetime of the membrane electrode. Therefore, there is a need to develop a highly efficient fuel cell anti-anode catalyst.
Disclosure of Invention
In view of this, the present embodiments provide a counter electrode PtIr/C alloy catalyst, a preparation method thereof, and application to a fuel cell, which achieve excellent counter electrode resistance and efficient counter electrode resistance.
In one aspect, a method for preparing a counter electrode PtIr/C alloy catalyst is provided, comprising: dissolving chloroplatinic acid and chloroiridium acid in deionized water according to a certain proportion to obtain a solution I, wherein the solution I is a mixed solution of the chloroplatinic acid and the chloroiridium acid;
adding graphitized carbon powder into the first solution to form a uniform second dispersion liquid, wherein at least part of platinum ions and at least part of iridium ions react with the carbon carrier and enter the pores of the carbon carrier or are adsorbed on the surface of the carbon carrier;
dissolving a reducing agent in deionized water, then uniformly dripping the solution into a dispersion liquid II for a co-reduction reaction, and obtaining solid powder III, wherein the solid powder III is a carbon carrier loaded Pt and Ir nanoparticle material through filtering, cleaning, drying and grinding;
and (3) placing the solid powder III in a reducing atmosphere containing at least carbon monoxide for high-temperature treatment, and cooling to obtain the antipodal PtIr/C alloy catalyst, wherein the antipodal PtIr/C alloy catalyst consists of a carbon carrier and nano-particles PtIr.
In some embodiments, chloroplatinic acid and chloroiridium acid are dissolved in deionized water according to a certain proportion to obtain a solution I, which comprises: and dissolving chloroplatinic acid and chloroiridium acid in a molar ratio of 1:1-5:1 in deionized water to obtain a solution I.
In some embodiments, adding graphitized carbon powder to the first solution to form a uniform second dispersion comprises: adding graphitized carbon powder into the solution I, and performing ultrasonic dispersion for 30-90 min to form uniform dispersion liquid II.
In some embodiments, the reducing agent is dissolved in deionized water, then uniformly added dropwise to the second dispersion for reduction, and the second dispersion is filtered, washed, dried and ground to obtain third solid powder, which comprises: dissolving a reducing agent in deionized water, uniformly dripping the solution into the dispersion liquid II through a separating funnel, carrying out reduction reaction for 30-120 min at the temperature of 30-90 ℃, and obtaining solid powder III through filtering, cleaning, drying and grinding.
In some embodiments, the solid powder III is subjected to high temperature treatment under a reducing atmosphere and cooled to obtain the anti-reverse PtIr/C alloy catalyst, which comprises: and (3) placing the solid powder III in a reaction furnace, treating at 300-700 ℃ for 3-8 hours under the reducing atmosphere, and then cooling to room temperature to obtain the antipole PtIr/C alloy catalyst.
In some embodiments, the graphitized carbon powder is one of EA carbon powder, carbon nanotubes, carbon nanofibers, graphene.
In some embodiments, the reducing agent is one of sodium borohydride, hydrazine hydrate, sodium citrate, glucose, ethanol.
In some embodiments, the rate of addition of the uniform drop to the second dispersion for the reduction reaction is from 1mL/min to 10mL/min.
In another aspect, a counter electrode PtIr/C alloy catalyst is provided, prepared by a method of preparing a counter electrode PtIr/C alloy catalyst according to any of the embodiments described above.
In yet another aspect, there is provided a use of a counter electrode PtIr/C alloy catalyst in a fuel cell, the counter electrode PtIr/C alloy catalyst prepared according to any of the above embodiments being used in a fuel cell.
Compared with the prior art, the beneficial effects that above-mentioned at least one technical scheme that this description embodiment adopted can reach include at least:
the following preparation processes are developed by utilizing the co-reduction and heat treatment modes: firstly, a platinum precursor and an iridium precursor with a certain concentration are mixed to form metal ions of Pt and Ir so as to be helpful for the adsorption of the carbon carrier to the metal ions;
then adding graphitized carbon powder into the mixed solution containing Pt and Ir, uniformly stirring and dispersing to form a dispersion liquid II, so that Pt ions and Ir ions are adsorbed in or on the carbon carrier, wherein the dispersion liquid II is different from the traditional physical adsorption or particle adsorption on the carbon carrier, and the compounds containing Pt and Ir can be more uniformly and efficiently introduced into pores of the carbon carrier or adsorbed on the surface of the carbon carrier through the mutual ion adsorption effect between in-situ reaction chemical bonds, namely the in-situ growth of PtIr nano particles is realized on the carbon carrier, the anchoring effect of the carbon carrier on the PtIr nano particles is facilitated, and the binding force is strong, so that the durability of the PtIr/C alloy catalyst on battery application can be improved;
on the basis, the dissolved reducing agent is uniformly dripped into the second dispersion liquid to carry out a co-reduction reaction, so that Pt and Ir are uniformly deposited on a carbon carrier together, the reaction speed is controlled and reduced, and agglomeration of particles is inhibited, so that a more uniform catalyst can be obtained;
finally, the high-temperature heat treatment is carried out in a reducing atmosphere with carbon monoxide, and under the high-temperature condition (for example, the temperature can be up to 700 ℃), the carbon monoxide can be adsorbed on the surface of PtIr nano particles to play a role in inhibiting particle agglomeration and growth, so that the alloying of Pt and Ir can be promoted, and the particle uniformity of the PtIr/C alloy catalyst can be further improved, and the obtained PtIr/C alloy catalyst shows excellent anti-counter-electrode performance and high-efficiency anti-counter-electrode efficiency when applied to a fuel cell.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present application, the drawings that are needed in the embodiments will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present application, and that other drawings can be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 is a TEM image of a PtIr/C alloy catalyst prepared in example 1 of the present application;
FIG. 2 is a TEM image of a PtIr/C alloy catalyst prepared according to example 2 of the present application;
FIG. 3 is a TEM image of a PtIr/C alloy catalyst prepared according to example 3 of the present application.
Detailed Description
Other advantages and effects of the present application will become apparent to those skilled in the art from the following disclosure, which describes the embodiments of the present application with reference to specific examples. It will be apparent that the described embodiments are only some, but not all, embodiments of the application. The application may be practiced or carried out in other embodiments that depart from the specific details, and the details of the present description may be modified or varied from the spirit and scope of the present application. It should be noted that the following embodiments and features in the embodiments may be combined with each other without conflict. All other embodiments, which can be made by those skilled in the art based on the embodiments of the application without making any inventive effort, are intended to be within the scope of the application.
It is noted that various aspects of the embodiments are described below within the scope of the following claims. It should be apparent that the aspects described herein may be embodied in a wide variety of forms and that any specific structure and/or function described herein is merely illustrative. Based on the present disclosure, one skilled in the art will appreciate that one aspect described herein may be implemented independently of any other aspect, and that two or more of these aspects may be combined in various ways. For example, apparatus may be implemented and/or methods practiced using any number and aspects set forth herein. In addition, such apparatus may be implemented and/or such methods practiced using other structure and/or functionality in addition to one or more of the aspects set forth herein. In addition, in the following description, specific details are provided in order to provide a thorough understanding of the examples. However, it will be understood by those skilled in the art that the present application may be practiced without these specific details.
In view of various adverse consequences caused by battery counter electrode in the background art, the inventor develops and obtains a high-efficiency counter electrode resistance PtIr/C alloy catalyst and a preparation method and application thereof through carrying out intensive research and improvement exploration on a counter electrode generating process and various catalyst schemes, and develops and obtains the preparation process by utilizing a co-reduction and heat treatment mode, wherein the application conception is as follows: firstly, a platinum precursor and an iridium precursor with a certain concentration are mixed to form metal ions of Pt and Ir so as to be helpful for the adsorption of the carbon carrier to the metal ions; then adding graphitized carbon powder into the mixed solution containing Pt and Ir, uniformly stirring and dispersing to form a dispersion liquid II, wherein the dispersion liquid II is different from the traditional physical adsorption or particle adsorption on a carbon carrier, and the compound containing Pt and Ir can be more uniformly and efficiently adsorbed on the carbon carrier through the mutual ion adsorption effect between in-situ reaction chemical bonds, namely, the in-situ growth of PtIr nano particles on the carbon surface is realized, the anchoring effect of the carbon carrier on the PtIr nano particles is facilitated, and the binding force is stronger.
Then on the basis, the dissolved reducing agent is uniformly dripped into the second dispersion liquid to carry out a co-reduction reaction, so that Pt and Ir are uniformly deposited on the carbon carrier together, the reaction speed is controlled and reduced, and the agglomeration of particles is inhibited, so that a more uniform catalyst can be obtained; finally, the high-temperature heat treatment is carried out in a reducing atmosphere with carbon monoxide, and under the high-temperature condition (for example, the temperature can be up to 700 ℃), the carbon monoxide can be adsorbed on the surface of PtIr nano particles to play a role in inhibiting particle agglomeration and growth, so that the alloying of Pt and Ir can be promoted, and the particle uniformity of the PtIr/C alloy catalyst can be further improved, and the obtained PtIr/C alloy catalyst shows excellent anti-counter-electrode performance and high-efficiency anti-counter-electrode efficiency when applied to a fuel cell.
Specifically, the preparation method of the anti-counter PtIr/C alloy catalyst provided by the embodiment of the application mainly comprises the following steps:
step 1, dissolving chloroplatinic acid and chloroiridium acid in deionized water according to a certain proportion to obtain a solution I, wherein the solution I is a mixed solution of the chloroplatinic acid and the chloroiridium acid;
step 2, graphitized carbon powder is added into the solution I to form a uniform dispersion liquid II, at least part of platinum ions and at least part of iridium ions interact with the carbon carrier, and enter the pores of the carbon carrier or are adsorbed on the surface of the carbon carrier;
step 3, dissolving a reducing agent in deionized water, then uniformly dripping the solution into a dispersion liquid II for co-reduction reaction, and obtaining solid powder III, wherein the solid powder III is a carbon carrier loaded Pt and Ir nanoparticle material through filtering, cleaning, drying and grinding;
and 4, placing the solid powder III in a reducing atmosphere for high-temperature treatment, and cooling to obtain the antipodal PtIr/C alloy catalyst, wherein the antipodal PtIr/C alloy catalyst consists of a carbon carrier and nano particles PtIr, and the particles are uniformly dispersed.
In some embodiments, step 1 above may be implemented as follows: and dissolving chloroplatinic acid and chloroiridium acid in a molar ratio of 1:1-5:1 in deionized water to obtain a solution I. In some embodiments, step 2 above may be implemented as follows: adding graphitized carbon powder into the solution I, and performing ultrasonic dispersion for 30-90 min to form uniform dispersion liquid II. Specifically, in some embodiments, the graphitized carbon powder herein may be selected from one of the following materials: carbon powder graphitized at high temperature, carbon nanotubes, carbon nanofibers, graphene.
In some embodiments, step 3 above may be implemented as follows: dissolving a reducing agent in deionized water, uniformly dripping the solution into the dispersion liquid II through a separating funnel, carrying out reduction reaction for 30-120 min at the temperature of 30-90 ℃, and obtaining solid powder III through filtering, cleaning, drying and grinding. Specifically, in some embodiments, the reducing agent may be selected from one of the following formulations: sodium borohydride, hydrazine hydrate, sodium citrate, glucose, and ethanol. In some embodiments, the rate of addition may be controlled, for example, by controlling an addition apparatus (e.g., an addition funnel) such that the solution of the reducing agent dissolved with deionized water is uniformly added to the second dispersion at a predetermined rate of addition. In some embodiments, the dropping rate may be controlled in the range of 1mL/min to 10mL/min, and the reaction rate may be controlled by controlling the dropping rate, thereby being more advantageous to obtain uniform nanoparticles.
In some embodiments, the above step 4 may be implemented as the following process: and (3) placing the solid powder III in a reaction furnace (such as a tube furnace), treating at 300-700 ℃ for 3-8 h under a reducing atmosphere, and then cooling to room temperature (25 ℃) to obtain the antipodal PtIr/C alloy catalyst. In some embodiments, this reducing atmosphere may comprise, in addition to carbon monoxide, at least one of the following: the argon, nitrogen, hydrogen and argon mixture may be fed into the reactor, for example, before the reaction starts.
In addition, in some embodiments, the present application also provides a counter electrode PtIr/C alloy catalyst, particularly, the catalyst is prepared by the preparation method of the counter electrode PtIr/C alloy catalyst according to any one of the embodiments. The prepared anti-counter PtIr/C alloy catalyst can be applied to fuel cells, for example, can be used as a core component of a proton exchange membrane fuel cell
The counter electrode PtIr/C alloy catalyst schemes provided by embodiments of the present application are more fully explained below by way of example in connection with several specific examples.
Example 1
Step 1, weighing 5.18g of chloroplatinic acid and 5.15g of chloroiridium acid, and dissolving in 500 mL deionized water to obtain a solution I (a mixed solution of the chloroplatinic acid and the chloroiridium acid);
step 2, weighing 4g of high-temperature graphitized carbon powder, adding the high-temperature graphitized carbon powder into the solution I (the mixed solution of chloroplatinic acid and chloroiridium acid), and performing ultrasonic dispersion for 60 minutes to form a uniform dispersion II (the mixed solution of the chloroplatinic acid and chloroiridium acid in which the high-temperature graphitized carbon powder is dispersed);
step 3, weighing 7.57g of sodium borohydride reducing agent, dissolving in 100mL of deionized water, controlling the dropping speed to be 2mL/min through a separating funnel, uniformly dropping into a second dispersion liquid, carrying out reduction reaction for 60min at 90 ℃, and obtaining solid powder III (high-temperature graphitized carbon loaded Pt and Ir nano-particle materials) through filtering, cleaning, drying and grinding;
and 4, placing the solid powder III in a tube furnace, treating for 6 hours at 500 ℃ under a mixed atmosphere of hydrogen and carbon monoxide, and cooling to room temperature of 25 ℃ to obtain the antipode PtIr/C alloy catalyst.
FIG. 1 is a TEM image of the PtIr/C alloy catalyst prepared in example 1 of the present application, and the catalyst is mainly composed of graphitized carbon as a carrier and nano particles PtIr, and the particles are uniformly dispersed, as observed by a microscope.
Example 2
Step 1, weighing 5.18g of chloroplatinic acid and 2.58g of chloroiridium acid, and dissolving in 500 mL deionized water to obtain a solution I (a mixed solution of the chloroplatinic acid and the chloroiridium acid);
step 2, weighing 4g of carbon nano tubes, adding the carbon nano tubes into the solution I (the mixed solution of chloroplatinic acid and chloroiridium acid), and performing ultrasonic dispersion for 30min to form uniform dispersion solution II (the mixed solution of the chloroplatinic acid and chloroiridium acid in which the carbon nano tubes are dispersed);
step 3, weighing 7.57g of hydrazine hydrate reducer, dissolving in 100mL of deionized water, controlling the dropping speed to be 1mL/min through a separating funnel, uniformly dropping into a second dispersion liquid, carrying out reduction reaction for 30min at 30 ℃, and obtaining solid powder three (carbon nano tube loaded Pt and Ir nano particle materials) through filtration, cleaning, drying and grinding;
and 4, placing the solid powder III in a tube furnace, treating at 700 ℃ for 8 hours under a mixed atmosphere of 5% argon and carbon monoxide, and cooling to room temperature of 25 ℃ to obtain the antipole PtIr/C alloy catalyst.
Fig. 2 is a TEM image of the PtIr/C alloy catalyst prepared in example 2 of the present application, which is mainly composed of carbon nanotubes and nanoparticles PtIr as carriers, and the particles are uniformly dispersed, as observed by a microscope.
Example 3
Step 1, weighing 5.18g of chloroplatinic acid and 5.15g of chloroiridium acid, and dissolving in 500 mL deionized water to obtain a solution I (a mixed solution of the chloroplatinic acid and the chloroiridium acid);
step 2, weighing 4g of graphene, adding the graphene into the first solution, and performing ultrasonic dispersion for 80 minutes to form a uniform dispersion liquid II (a mixed solution of chloroplatinic acid and chloroiridium acid in which the graphene is dispersed);
step 3, weighing 7.57g of sodium citrate reducer, dissolving in 100mL of deionized water, controlling the dropping speed to be 5mL/min through a separating funnel, uniformly dropping into the solution B, carrying out reduction reaction for 120min at 90 ℃, and obtaining solid powder three (graphene loaded Pt and Ir nanoparticle materials) through filtration, cleaning, drying and grinding;
and 4, placing the solid powder III in a tube furnace, treating for 3 hours at 500 ℃ in a mixed gas atmosphere of 10% hydrogen-argon mixed gas and carbon monoxide, and cooling to room temperature of 25 ℃ to obtain the antipole PtIr/C alloy catalyst.
Fig. 3 is a TEM image of the PtIr/C alloy catalyst prepared in example 3 of the present application, and the catalyst is mainly composed of graphene as a carrier and nano-particles PtIr, and the particles are uniformly dispersed, as observed by a microscope.
Example 4
Step 1, weighing 5.18g of chloroplatinic acid and 5.15g of chloroiridium acid, and dissolving in 500 mL deionized water to obtain a solution I (a mixed solution of the chloroplatinic acid and the chloroiridium acid);
step 2, weighing 4g of carbon nano fibers, adding the carbon nano fibers into the first solution, and performing ultrasonic dispersion for 60min to form a uniform dispersion liquid II (a mixed solution of chloroplatinic acid and chloroiridium acid in which the carbon nano fibers are dispersed);
step 3, weighing 7.57g of ethanol reducer, dissolving in 100mL of deionized water, controlling the dropping speed to be 5mL/min through a separating funnel, uniformly dropping into a second dispersion liquid, carrying out reduction reaction for 70min at 30 ℃, and obtaining solid powder three (carbon nanofiber loaded Pt and Ir nanoparticle materials) through filtration, cleaning, drying and grinding;
and 4, placing the solid powder III in a tube furnace, treating for 6 hours at 600 ℃ in a carbon monoxide atmosphere, and cooling to room temperature of 25 ℃ to obtain the antipode PtIr/C alloy catalyst.
Example 5
Step 1, weighing 5.18g of chloroplatinic acid and 5.15g of chloroiridium acid, and dissolving in 500 mL deionized water to obtain a solution I (a mixed solution of the chloroplatinic acid and the chloroiridium acid);
step 2, weighing 4g of graphene, adding the graphene into the first solution, and performing ultrasonic dispersion for 60min to form a uniform dispersion liquid II (a mixed solution of chloroplatinic acid and chloroiridium acid in which the graphene is dispersed);
step 3, weighing 7.57g of glucose reducer, dissolving in 100mL of deionized water, controlling the dropping speed to be 2mL/min through a separating funnel, uniformly dropping into a second dispersion liquid, carrying out reduction reaction for 60min at 30 ℃, and obtaining solid powder III (graphene loaded Pt and Ir nano-particle materials) through filtration, cleaning, drying and grinding;
and 4, placing the solid powder C in a tube furnace, treating for 6 hours at 500 ℃ under a mixed atmosphere of nitrogen and carbon monoxide, and cooling to room temperature to obtain the antipodal PtIr/C alloy catalyst.
Comparative example 1
The difference from example 1 is only that the dropping rate is 30mL/min when the reducing agent is dropped, and the specific steps are as follows:
step 1, weighing 5.18g of chloroplatinic acid and 5.15g of chloroiridium acid, and dissolving in 500 mL deionized water to obtain a solution I (a mixed solution of the chloroplatinic acid and the chloroiridium acid);
step 2, weighing 4g of high-temperature graphitized carbon powder, adding the high-temperature graphitized carbon powder into the first solution, and performing ultrasonic dispersion for 60min to form a uniform dispersion liquid II (high-temperature graphitized carbon loaded Pt and Ir nanoparticle materials);
step 3, weighing 7.57g of sodium borohydride reducing agent, dissolving in 100mL of deionized water, controlling the dropping speed to be 30mL/min through a separating funnel, uniformly dropping into a second dispersion liquid, carrying out reduction reaction for 60min at 90 ℃, and obtaining solid powder III (high-temperature graphitized carbon loaded Pt and Ir nano-particle materials) through filtering, cleaning, drying and grinding;
and 4, placing the solid powder III in a tube furnace, treating for 6 hours at 500 ℃ in a hydrogen atmosphere, and cooling to room temperature of 25 ℃ to obtain the antipode PtIr/C alloy catalyst.
Comparative example 2
The only difference from example 1 is that the heat treatment temperature in step 4 was changed from 500 ℃ to 200 ℃, the specific steps were as follows:
step 1, weighing 5.18g of chloroplatinic acid and 5.15g of chloroiridium acid, and dissolving in 500 mL deionized water to obtain a solution I (a mixed solution of the chloroplatinic acid and the chloroiridium acid);
step 2, weighing 4g of high-temperature graphitized carbon powder, adding the high-temperature graphitized carbon powder into the first solution, and performing ultrasonic dispersion for 60min to form a uniform dispersion liquid II (high-temperature graphitized carbon loaded Pt and Ir nanoparticle materials);
step 3, weighing 7.57g of sodium borohydride reducing agent, dissolving in 100mL of deionized water, controlling the dropping speed to be 2mL/min through a separating funnel, uniformly dropping into a second dispersion liquid, carrying out reduction reaction for 60min at 90 ℃, and obtaining solid powder III (high-temperature graphitized carbon loaded Pt and Ir nano-particle materials) through filtering, cleaning, drying and grinding;
and 4, placing the solid powder III in a tube furnace, treating for 6 hours at 200 ℃ in a hydrogen atmosphere, and cooling to room temperature of 25 ℃ to obtain the antipode PtIr/C alloy catalyst.
TABLE 1
Table 1 above shows the comparative data of the particle size and the anti-counter time of the catalysts prepared in examples 1-5 and comparative examples 1 and 2, and shows that the counter time of the PtIr/C catalyst prepared in examples 1-5 is 75-135min, which is significantly higher than that of the PtIr/C catalyst prepared in comparative examples 1-2 by 60-65min, and that the anti-counter PtIr/C alloy catalyst prepared by the preparation process of the present application has higher anti-counter efficiency and excellent anti-counter performance.
In this specification, identical and similar parts of the embodiments are referred to each other, and each embodiment focuses on the differences from the other embodiments. Meanwhile, the specification uses specific words to describe the embodiments of the specification. Reference to "one embodiment," "an embodiment," and/or "some embodiments" means that a particular feature, structure, or characteristic is associated with at least one embodiment of the present description. Thus, it should be emphasized and should be appreciated that two or more references to "an embodiment" or "one embodiment" or "an alternative embodiment" in various positions in this specification are not necessarily referring to the same embodiment. Furthermore, certain features, structures, or characteristics of one or more embodiments of the present description may be combined as suitable.
Furthermore, the order in which the elements and sequences are processed, the use of numerical letters, or other designations in the description are not intended to limit the order in which the processes and methods of the description are performed unless explicitly recited in the claims. While certain presently useful inventive embodiments have been discussed in the foregoing disclosure, by way of various examples, it is to be understood that such details are merely illustrative and that the appended claims are not limited to the disclosed embodiments, but, on the contrary, are intended to cover all modifications and equivalent arrangements included within the spirit and scope of the embodiments of the present disclosure. For example, while the system components described above may be implemented by hardware devices, they may also be implemented solely by software solutions, such as installing the described system on an existing processing device or mobile device.
While the basic concepts have been described above, it will be apparent to those skilled in the art that the foregoing detailed disclosure is by way of example only and is not intended to be limiting. Although not explicitly described herein, various modifications, improvements, and adaptations to the present disclosure may occur to one skilled in the art. Such modifications, improvements, and modifications are intended to be suggested within this specification, and therefore, such modifications, improvements, and modifications are intended to be included within the spirit and scope of the exemplary embodiments of the present application.
Claims (10)
1. A method for preparing a counter electrode resistance PtIr/C alloy catalyst, which is characterized by comprising the following steps:
dissolving chloroplatinic acid and chloroiridium acid in deionized water according to a certain proportion to obtain a solution I, wherein the solution I is a mixed solution of the chloroplatinic acid and the chloroiridium acid;
adding graphitized carbon powder into the first solution to form a uniform second dispersion liquid, wherein at least part of platinum ions and at least part of iridium ions react with the carbon carrier and enter the pores of the carbon carrier or are adsorbed on the surface of the carbon carrier;
dissolving a reducing agent in deionized water, then uniformly dripping the solution into a dispersion liquid II for a co-reduction reaction, and obtaining solid powder III, wherein the solid powder III is a carbon carrier loaded Pt and Ir nanoparticle material through filtering, cleaning, drying and grinding;
and (3) placing the solid powder III in a reducing atmosphere containing at least carbon monoxide for high-temperature treatment, and cooling to obtain the antipodal PtIr/C alloy catalyst, wherein the antipodal PtIr/C alloy catalyst consists of a carbon carrier and nano-particles PtIr.
2. The method of claim 1, wherein dissolving chloroplatinic acid and chloroiridium acid in deionized water according to a ratio provides a solution one comprising:
and dissolving chloroplatinic acid and chloroiridium acid in a molar ratio of 1:1-5:1 in deionized water to obtain a solution I.
3. The method of claim 1, wherein adding graphitized carbon powder to the first solution to form a uniform second dispersion comprises:
adding graphitized carbon powder into the solution I, and performing ultrasonic dispersion for 30-90 min to form uniform dispersion liquid II.
4. The preparation method according to claim 1, wherein the reducing agent is dissolved in deionized water, and then uniformly added dropwise to the second dispersion for reduction reaction, and the third solid powder is obtained by filtration, washing, drying and grinding, comprising:
dissolving a reducing agent in deionized water, uniformly dripping the solution into the dispersion liquid II through a separating funnel, carrying out reduction reaction for 30-120 min at the temperature of 30-90 ℃, and obtaining solid powder III through filtering, cleaning, drying and grinding.
5. The preparation method according to claim 1, wherein the solid powder III is subjected to high temperature treatment in a reducing atmosphere and cooled to obtain the antipodal PtIr/C alloy catalyst, comprising:
and (3) placing the solid powder III in a reaction furnace, treating at 300-700 ℃ for 3-8 hours under the reducing atmosphere, and then cooling to room temperature to obtain the antipole PtIr/C alloy catalyst.
6. The method of claim 1, wherein the graphitized carbon powder is one of EA carbon powder, carbon nanotubes, carbon nanofibers, and graphene.
7. The method according to claim 1, wherein the reducing agent is one of sodium borohydride, hydrazine hydrate, sodium citrate, glucose, and ethanol.
8. The method according to claim 1, wherein the dripping rate of the solution to be uniformly dripped into the second dispersion for the reduction reaction is 1mL/min to 10mL/min.
9. A counter electrode PtIr/C alloy catalyst prepared by the process for preparing a counter electrode PtIr/C alloy catalyst according to any one of claims 1 to 8.
10. Use of a counter electrode PtIr/C alloy catalyst in a fuel cell, characterized in that the counter electrode PtIr/C alloy catalyst prepared according to claim 9 is applied to a fuel cell.
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