CN113363512A - Mixed oxide multifunctional electrocatalytic material and preparation method and application thereof - Google Patents
Mixed oxide multifunctional electrocatalytic material and preparation method and application thereof Download PDFInfo
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Abstract
The invention provides a mixed oxide multifunctional electrocatalytic material, which belongs to the technical field of electrocatalytic materials and consists of a metal oxide A with oxygen storage capacity and a metal oxide B with oxygen precipitation reaction catalytic activity; the coordination of the metal oxide A with oxygen storage capacity and the metal oxide B with oxygen precipitation reaction catalytic activity can relieve the poisoning of carbon monoxide to a catalyst, weaken the damage of free radicals to a proton exchange membrane, protect a carbon carrier and a catalytic layer through electrolyzed water when an electric fuel cell stack generates reverse polarity, improve the stability of a catalytic material, and play a positive role in improving the catalytic performance of the catalytic material; the invention also provides a preparation method and application of the mixed oxide multifunctional electrocatalytic material.
Description
Technical Field
The invention relates to the technical field of electrocatalytic materials, in particular to a mixed oxide multifunctional electrocatalytic material and a preparation method and application thereof.
Background
The fuel cell is an energy conversion device, can directly convert chemical energy in fuel into electric energy and heat energy through electrochemical oxidation-reduction reaction, and has the advantages of high conversion efficiency and environmental protection. The hydrogen can be widely applied to a series of fields such as spaceflight, military submarines, transportation, portable electronic equipment, fixed power stations and the like, and is matched with hydrogen prepared from renewable clean energy to be used, so that the energy crisis can be relieved, and the emission of pollutants can be reduced.
For pem fuel cells, the most critical component is the membrane electrode assembly. Wherein the membrane electrode assembly is positioned at the middle most part of the membrane electrode assembly and is used for conducting protons; the catalyst layers are arranged at two sides of the proton exchange membrane and are tightly attached to the proton exchange membrane, and the catalyst layers contain catalytic materials for catalyzing electrochemical oxidation-reduction reaction and are places for converting chemical energy into electric energy. Currently, platinum-containing catalysts supported on carbon materials are predominant. And the membrane electrode assembly can be combined with corresponding accessories to form a single cell. However, the voltage of a single fuel cell is limited, and therefore, a certain number of fuel cells are usually connected in series to form a stack.
The fuel cell stack needs stable and appropriate conditions in the operation process, but under the actual use working condition, particularly when the fuel cell stack is applied to a transportation vehicle, the stack can be subjected to multiple start-stop and frequent load changes, which can possibly cause the fuel cell to generate a reverse pole phenomenon, the phenomenon can cause corrosion of a carbon carrier in a catalyst layer of the fuel cell, the corrosion of the carbon carrier can cause the structure collapse of the catalyst layer, and nanoparticles of active substances such as platinum fall off and agglomerate, so that the electrochemical active area is reduced. In addition, the hydrophilicity and hydrophobicity and the porosity of the catalytic layer structure may also be changed to cause performance degradation. If the reverse polarity time is long enough, oxidation and accelerated degradation of the microporous layer and proton exchange membrane adjacent to the catalytic layer may also occur, resulting in a drop in open circuit voltage and even a short circuit. The end result can be reduced performance and even failure damage of the stack.
In addition, in the hydrogen-oxygen fuel cell, the catalyst in the catalyst layer also generates hydrogen peroxide in the process of catalyzing hydrogen oxidation and oxygen reduction, and the hydrogen peroxide is further converted into hydroxyl radical (OH), peroxyl radical (OOH) and other substances, which attack the proton exchange membrane to cause chemical degradation of the proton exchange membrane, so that the performance and the service life of the proton exchange membrane are reduced, and finally, the performance and the service life of the fuel cell stack are also reduced.
In addition, for a hydrogen-oxygen fuel cell, the fuel at the anode is hydrogen. At present, hydrogen is mainly converted from fossil fuels such as natural gas, coal and petroleum, and the purity of the hydrogen is often insufficient, and the hydrogen usually contains a certain amount of carbon monoxide, and even after multi-step purification, the carbon monoxide still has about 10ppm of carbon monoxide. Even trace amounts (ppm levels) of carbon monoxide can result in the active sites of the anode platinum-containing catalyst in a hydrogen-oxygen fuel cell being occupied, significantly reducing the output power and efficiency of the fuel cell. In summary, the above three problems significantly affect the performance and lifetime of a fuel cell stack, and are challenges in fuel cell applications.
In the case of the fuel cell reverse polarity phenomenon, researchers generally add catalytic components for oxygen evolution reaction, such as iridium oxide and ruthenium oxide, to promote electrolysis of water during reverse polarity to protect the carbon carrier and retard corrosion of the carbon carrier. For example, there are a number of patents by kingdom zhuangyufeng (Johnson Matthey) and barard corporation, canada (Ballard Power Systems Inc.) that relate to catalytic layers and membrane electrode assemblies that contain catalysts for oxygen evolution reactions, and fuel cells that include such catalytic layers and membrane electrode assemblies. Typically, for example, US20170033369a1, relates to a catalytic layer which, in addition to a platinum-containing catalyst, a carbon support and a proton exchange membrane, is supplemented with an oxygen evolution reaction catalyst. The catalytic layer has better resistance under the condition of high voltage (reverse polarity or start-stop condition);
for the stability problem of the proton exchange membrane, the corrosion of the proton exchange membrane by the free radicals can be slowed down to some extent by adding various free radical scavengers in the proton exchange membrane, for example, U.S. Pat. nos. US20070212593a1 and US20120045704a1 disclose a stable proton exchange membrane and a membrane electrode, respectively, which all improve the resistance of the proton exchange membrane to peroxide free radicals by adding active components in the proton exchange membrane. Common free radical scavengers include various metal ions and metal oxides such as Ce3+、Ce4+、Mn2+、Mn4+、Co2+、Co3+Plasma metal ion and CeO2、MnO2、Mn2O3、CoO、CoO2、TiO2、Fe2O3And oxides such as FeO.
In order to solve the problem of carbon monoxide poisoning, researchers generally form platinum and other metals into an alloy or introduce metal oxides, and the like, so that the oxidation of CO is promoted and the adsorption strength of CO is weakened through a bifunctional mechanism or a ligand effect to inhibit the poisoning effect of CO. The common method comprises preparing carbon-supported bimetallic catalysts such as PtRu/C, PtNi/C, PtIr/C and PtSn/C, and introducing CeO into the catalysts2、FeOx、WOxAnd the like. For example, U.S. Pat. No. 4, 20060258527, 1 discloses a PtAu-M with carbon monoxide tolerancexOya/C supported catalyst;
however, the efficiency and the lifetime of the fuel cell are closely related to the anti-reversal capability of the catalyst layer, the stability of the proton exchange membrane and the carbon monoxide tolerance capability of the platinum-containing catalyst, and a solution to a certain problem is not able to solve the performance and lifetime problems of the fuel cell well, but there are few solutions that can solve or alleviate the above three problems at the same time.
In response to the above problems, US20210013519a1 and the corresponding chinese patent CN111868307A disclose a membrane electrode assembly comprising ceria supporting an oxide comprising iridium. By introducing the ceria-supported iridium oxide-containing material into the catalytic layer, the life and stability of the fuel cell membrane electrode and the stack are improved. However, considering that pure ceria has insufficient stability and is easily dissolved in the electrochemical environment of the fuel cell membrane electrode, the stability of the material can be improved to some extent by supporting the iridium-containing oxide on the surface of ceria.
Disclosure of Invention
The present invention is directed to overcoming at least one of the above-mentioned deficiencies in the prior art and providing a mixed oxide multifunctional electrocatalytic material having better free radical scavenging ability, reduced carbon monoxide poisoning, reduced antipole phenomena and improved catalytic material stability.
The invention also aims to provide a preparation method of the mixed oxide multifunctional electrocatalytic material.
The invention also aims to provide application of the mixed oxide multifunctional electrocatalytic material.
The invention adopts the technical scheme that the mixed oxide multifunctional electrocatalytic material consists of a metal oxide A with oxygen storage capacity and a metal oxide B with oxygen precipitation reaction catalytic activity.
The multifunctional electrocatalytic material is applied to a hydrogen-oxygen fuel cell as a catalyst in a catalyst layer, and consists of a metal oxide A with oxygen storage capacity and a metal oxide B with oxygen precipitation reaction catalytic activity, wherein the oxide A with oxygen storage capacity has the functions of eliminating free radicals and reducing carbon monoxide poisoning; the oxide B with the catalytic activity of oxygen precipitation reaction has the water electrolysis capacity, and can reduce the damage of the reverse pole phenomenon to the catalytic layer and other components of the fuel cell when the fuel cell stack generates reverse pole; the coordination of the metal oxide A with oxygen storage capacity and the metal oxide B with oxygen precipitation reaction catalytic activity can relieve the poisoning of carbon monoxide to the catalyst, weaken the damage of free radicals to a proton exchange membrane, protect a carbon carrier and a catalytic layer through electrolyzed water when an electric fuel cell stack generates reverse polarity, improve the stability of the catalytic material, and play a positive role in improving the catalytic performance of the catalytic material.
In the multifunctional electrocatalytic material of the invention, the metal oxide A or the metal oxide B is contained in the catalyst working process, wherein the metal acts through the form of metal ions, such as metal ions, and the multifunctional electrocatalytic material exists in the form of iridium oxide which has stronger anti-polarity capability relative to iridium metal; in addition, the present invention is a non-supported catalyst, and the non-supported catalyst has less influence on each substance in the catalyst layer than the supported catalyst when the catalyst is added as an additive to the catalyst layer.
Further, the metal oxide A is an oxide of cerium, and the metal oxide B is an oxide of iridium and/or ruthenium.
Preferably, the metal oxide A is one or more of cerium dioxide, cerium oxide, doped cerium dioxide and doped cerium oxide; and/or the metal oxide B is one or a mixture of iridium oxide, ruthenium oxide and ruthenium iridium oxide.
Further, in the electrocatalytic material, the mass fraction of the metal oxide B is 20-90%.
Preferably, in the electrocatalytic material, the mass component of the metal oxide B is 40-70%. The reasonable proportion is designed, which is beneficial to simultaneously and maximally exerting the carbon monoxide poisoning resistance and the free radical resistance of the metal oxide A and the antipole resistance of the metal oxide B.
Further, the doping element in the doped cerium oxide and the doped cerium trioxide is one or more of transition metal elements or lanthanide metal elements.
The doping of the transition metal element or the lanthanide series metal element is beneficial to improving the stability of the oxide A with the oxygen storage capacity, and plays a positive role in improving the free radical eliminating capacity and the carbon monoxide poisoning resistance of the oxide A with the oxygen storage capacity.
Preferably, the doping element in the doped cerium oxide and doped cerium oxide is one or more of Mn, Cu, Ti, Pr, Gd and Zr.
Further, the doping element in the doped cerium dioxide and doped cerium sesquioxide is one or more of Pr, Gd and Zr.
More preferably, the atomic mass of the doping element in the doped cerium dioxide and the doped cerium trioxide is 1-20% of the atomic mass of cerium.
Dissolving a water-soluble compound containing cerium and/or a water-soluble compound containing cerium and a doping element, carrying out a first hydrothermal reaction, washing and drying; and adding an iridium-containing water-soluble compound or a ruthenium-iridium-containing water-soluble compound, uniformly mixing, carrying out a second hydrothermal reaction, carrying out suction filtration and washing to obtain a precipitate, drying the precipitate, and calcining to obtain the mixed oxide multifunctional electrocatalytic material.
The preparation process of the electrocatalytic material adopts a two-step hydrothermal method, aiming at the catalytic material, cerium hydroxide is prepared by the first step of hydrothermal reaction, and cerium ions and iridium ions released from the cerium hydroxide react with hydroxide radical under the alkaline environment to form homogeneous nucleation together in the second step of hydrothermal reaction, so that atomic-level or molecular-level mixed CeO is formedx-IrO2In the subsequent heat treatment process, in the process of dehydrating the hydroxide of cerium and the hydroxide of iridium to form oxide, the amorphous compound not only has the self-condensation dehydration process of the hydroxide of iridium and the hydroxide of cerium, but also has the co-dehydration condensation process of the hydroxide of iridium and the hydroxide of cerium to form an iridium-oxygen-cerium bonding structure, further promotes the uniform mixing of cerium and iridium, and can form amorphous and crystalline multiphase nano-materials after heat treatment, thereby having both stability and high activity. Therefore, compared with the catalyst prepared by the one-step hydrothermal method, the catalyst prepared by the two-step hydrothermal method has better dispersity and higher uniformity.
Further, the specific steps are as follows:
s1, dissolving a water-soluble compound containing cerium and/or a water-soluble compound containing cerium and doping elements in water to form a solution, and then mixing the solution and an alkali metal hydroxide aqueous solution with a certain concentration in a polytetrafluoroethylene reaction kettle to form a uniform solution;
s2: placing the reaction kettle in the S1 in an oven, preserving heat for 12-24 hours at 100-180 ℃, washing and filtering a product for 2-5 times by using water and ethanol after the hydrothermal reaction is finished, and then drying the product in the oven for a period of time;
s3: adding the dried product in S2 into an alkali metal hydroxide solution with a certain concentration, uniformly mixing, adding a water-soluble compound containing iridium or a water-soluble compound containing ruthenium and iridium, mixing, and transferring to a polytetrafluoroethylene reaction kettle to form a uniform solution;
s4: and (3) placing the reaction kettle in S3 in an oven, preserving heat for 12-24 h at the temperature of 100-.
Further, the water-soluble compound of cerium is selected from one or more of cerium nitrate, cerium chloride and cerium acetate, the water-soluble compound of iridium is selected from one or more of iridium trichloride, iridium tetrachloride, chloroiridic acid and sodium chloroiridate, and the alkali metal hydroxide is one or two of sodium hydroxide and potassium hydroxide.
A mixed oxide multifunctional electrocatalytic material as described above, which can be used to make up a membrane electrode assembly; the membrane electrode assembly can be used as a composition basis of a fuel cell stack.
Compared with the prior art, the invention has the beneficial effects that:
(1) the multifunctional electro-catalytic material provided by the invention consists of a metal oxide A with oxygen storage capacity and a metal oxide B with oxygen precipitation reaction catalytic activity, can simultaneously improve the antipole resistance of the catalyst, the stability of a proton exchange membrane, the carbon monoxide tolerance of a platinum-containing catalyst and the stability of the catalyst material, and has a positive effect on improving the catalytic performance of the catalyst material.
(2) The doped metal oxide a can further improve the radical scavenging ability and also play a positive role in the resistance against carbon monoxide poisoning.
(3) The preparation of the multifunctional electrocatalytic material adopts a two-step hydrothermal method, and aiming at the catalytic material related to the invention, the dispersibility and the uniformity of the material prepared by the two-step method are superior to those of the one-step hydrothermal method.
Drawings
FIG. 1 shows that the ratio of the noble metal pure iridium oxide SA100 electrocatalytic material in the invention in example 1 and comparative example 1 is 0.5M H2SO4Linear scan voltammogram of (1).
Fig. 2 is a bar graph comparing fluoride ion release rates in Fenton experiments for example 1 of the present invention with comparative example 2 (Meclin commercial 20nm ceria (C804512, 99.5%) catalytic material) and a blank sample.
Detailed Description
The examples of the present invention are provided for illustrative purposes only and are not to be construed as limiting the invention.
Example 1
The preparation of the mixed oxide multifunctional electrocatalytic material comprises the following steps:
0.868g Ce (NO)3)3·6H2O was dissolved in 5mL of water, and a certain amount of 0.21g NaOH was dissolved in 35mL of water. Mixing the two solutions in a polytetrafluoroethylene reaction kettle, and magnetically stirring for 30 min. The reaction vessel was then placed in an oven and incubated at 100 ℃ for 24 h. After the hydrothermal reaction is finished, the product is washed and filtered for 3 times by using water and ethanol, and then dried in an oven at 60 ℃ for about 30 min. Then 30mg of the product was weighed out and added to 20mL of 0.1M NaOH solution and the mixture was sonicated for at least 30min to ensure uniform mixing. 0.0735g of H were then added2IrCl6·6H2O (35 wt% Ir) precursor was added to the solution. The solution was transferred to a 40mL teflon reaction kettle and then sonicated for about 10min to form a homogeneous solution. The reaction kettle is placed in an oven and kept at 150 ℃ for 720 min. Washing with suction filtration twice to obtain precipitate, and drying the precipitate at 60 deg.CDrying for at least 30min, and calcining the obtained product at 400 ℃ for 2h to obtain the final product, wherein the designed content of iridium oxide is 50%.
Example 2
0.868g Ce (NO)3)3·6H2O was dissolved in 5mL of water, and a certain amount of 0.21g NaOH was dissolved in 35mL of water. Mixing the two solutions in a polytetrafluoroethylene reaction kettle, and magnetically stirring for 30 min. The reaction vessel was then placed in an oven and incubated at 100 ℃ for 24 h. After the hydrothermal reaction is finished, the product is washed and filtered for 3 times by using water and ethanol, and then dried in an oven at 60 ℃ for about 30 min. Then 30mg of the product was weighed out and added to 20mL of 0.1M NaOH solution and the mixture was sonicated for at least 30min to ensure uniform mixing. 0.0558g of H were then added2IrCl6·6H2O (35 wt% Ir) precursor was added to the solution. The solution was transferred to a 40mL teflon reaction kettle and then sonicated for about 10min to form a homogeneous solution. The reaction kettle is placed in an oven and kept at 150 ℃ for 720 min. And (3) obtaining a precipitate through two times of suction filtration and washing, drying the precipitate at 60 ℃ for at least 30min, and finally calcining the obtained product at 400 ℃ for 2h to obtain a final product, wherein the designed content of iridium oxide is 40%.
Example 3
0.868g Ce (NO)3)3·6H2O was dissolved in 5mL of water, and a certain amount of 0.21g NaOH was dissolved in 35mL of water. Mixing the two solutions in a polytetrafluoroethylene reaction kettle, and magnetically stirring for 30 min. The reaction vessel was then placed in an oven and incubated at 100 ℃ for 24 h. After the hydrothermal reaction is finished, the product is washed and filtered for 3 times by using water and ethanol, and then dried in an oven at 60 ℃ for about 30 min. Then 30mg of the product was weighed out and added to 20mL of 0.1M NaOH solution and the mixture was sonicated for at least 30min to ensure uniform mixing. 0.0882g of H were then added2IrCl6·6H2O (35 wt% Ir) precursor was added to the solution. The solution was transferred to a 40mL teflon reaction kettle and then sonicated for about 10min to form a homogeneous solution. The reaction kettle is placed in an oven and kept at 150 ℃ for 720 min. Washing with suction filtration twice to obtain precipitate, and drying the precipitate at 60 deg.CAnd (3) 30min, and finally calcining the obtained product at 400 ℃ for 2h to obtain a final product, wherein the designed content of iridium oxide is 60%.
Example 4
0.868g Ce (NO)3)3·6H2O and 0.162g Zr (NO)3)4Dissolved in 5mL of water and a defined amount of 0.21g NaOH dissolved in 35mL of water. Mixing the two solutions in a polytetrafluoroethylene reaction kettle, and magnetically stirring for 30 min. The reaction vessel was then placed in an oven and incubated at 100 ℃ for 24 h. After the hydrothermal reaction is finished, washing and filtering the product by using water and ethanol for 3 times, and then drying in an oven at 60 ℃ for about 30min to obtain the 10% zirconium-doped cerium oxide. Then 30mg of the product was weighed out and added to 20mL of 0.1M NaOH solution and the mixture was sonicated for at least 30min to ensure uniform mixing. 0.0735g of H were then added2IrCl6·6H2O (35 wt% Ir) precursor was added to the solution. The solution was transferred to a 40mL teflon reaction kettle and then sonicated for about 10min to form a homogeneous solution. The reaction kettle is placed in an oven and kept at 150 ℃ for 720 min. And (3) obtaining a precipitate through two times of suction filtration and washing, drying the precipitate at 60 ℃ for at least 30min, and finally calcining the obtained product at 400 ℃ for 2h to obtain a final product, wherein the designed content of iridium oxide is 50%.
Oxygen evolution reaction test of the mixed oxide multifunctional electrocatalytic material:
the anti-reverse-polarity effect of the catalytic material is mainly realized by preventing the carbon carrier in the carbon-supported platinum catalyst from being corroded by catalyzing and electrolyzing water through the catalytic material. Therefore, the electrolytic water performance of the catalytic material is closely related to the anti-reversal pole capability, and the overpotential of the oxygen precipitation reaction in the electrolytic water is higher and is a key reaction for determining the catalytic performance of the electrolytic water. Generally, the higher the catalytic activity of the catalytic material for oxygen evolution reaction, the higher the catalytic performance of electrolyzed water, and thus the stronger the anti-reversal capability of the material. This section characterizes the material's resistance to reversal by catalytic activity on the oxygen evolution reaction of the catalytic material.
Respectively dispersing the catalytic materials prepared in the embodiments 1-4 in the mixed solution of water and isopropanol, and adding a certain amount of the catalytic materials
The solution is ultrasonically dispersed to obtain evenly dispersed slurry, a certain amount of the slurry is dripped on a rotating disc gold electrode to prepare a working electrode, the surface of the electrode is counted by iridium metal, and the loading capacity is 0.099mgIr/cm2。
The electrode was dried and then saturated with nitrogen at 0.5M H2SO4Linear sweep voltammetry was performed in the electrolyte using a three-electrode system with the reference electrode being a mercury-mercurous sulfate electrode and the counter electrode being a platinum sheet electrode at a sweep rate of 5mV/s, with the results shown in example 1 of FIG. 1, the home-made catalyst of example 1 was run at 10mA/cm2The overpotential at the current density was 315 mV. As a comparison, a commercial anti-reverse-polarity iridium oxide catalyst (iridium oxide content 100%) was introduced as comparative example 1, see comparative example 1 in FIG. 1, commercial anti-reverse-polarity iridium oxide catalyst comparative example 1 at 10mA/cm2The overpotential at the current density was 329 mV. The catalyst prepared in example 1 is clearly superior to the commercial iridium oxide catalyst in terms of overpotential.
The results of the oxygen evolution reaction tests of examples 1 to 4 show that the anti-reversal capability is stronger as the content of iridium oxide increases, but the anti-carbon monoxide capability and the anti-radical capability are correspondingly reduced. The preferred iridium oxide content is 40-70%. The cerium oxide doped with other elements can improve the stability of the catalytic material, and can also have beneficial effects on the counter-electrode resistance, the carbon monoxide poisoning resistance and the free radical resistance of the material.
Fenton experiment:
as mentioned above, in the hydrogen-oxygen fuel cell, the catalyst in the catalytic layer generates hydrogen peroxide during the catalytic process, and the hydrogen peroxide is further converted into hydroxyl radical (OH), peroxyl radical (OOH), and other substances, which attack the proton exchange membrane to cause chemical degradation of the proton exchange membrane. The damage of the proton membrane by the free radicals can be relieved by adding the free radical eliminator. The Fenton experiment can be used for comparing the free radical eliminating capacity of the catalytic material, namely the protection capacity of the catalytic material on the proton exchange membrane.
Specifically, ferrous sulfate and hydrogen peroxide solution are used for preparing 5 percent of hydrogen peroxide by mass fraction and Fe2+5ppm Fenton reagent. Cutting into three parts of 4 x 5cm
211 proton exchange membrane. Three portions of Fenton reagent, each 100mL, were weighed. The proton exchange membrane and the 100mL Fenton were packed separately into three containers. In a container with one part of Fenton's reagent and proton membrane was added 5mg of the multifunctional electrocatalyst prepared in example 1. In another Fenton reagent and proton membrane vessel, 5mg of 20nm commercial ceria (ceria content 100%) was added as the catalyst of comparative example 2. The third Fenton reagent and proton membrane vessel was empty without any catalytic material. The three containers are placed in a water bath environment at 80 ℃ and stirred and heated for 6 hours. After six hours, the Fenton reagent was cooled, 30mL of the solution was taken out and mixed with 30mL of the TISAB buffer solution, and the fluorine ion content was measured with a fluorine ion electrode to calculate the fluorine ion release rate. The results are shown in FIG. 2, from which it can be seen that the fluoride ion release rate was 0.16mg F compared to the blank experiment without any catalytic material added-A polymer in g. Comparative example 2 for comparison, the fluoride ion release rate was 0.1mg F-The polymer has certain free radical removing capacity. In the experiment involving the multifunctional electrocatalytic material in the embodiment 1 of the present invention, the release rate of fluorine ions was 0.074mg F-The/g polymer shows better free radical scavenging capacity and can better protect a proton exchange membrane. The catalytic material prepared in example 2, which has a lower fluoride ion release rate after the Fenton experiment, has a lower iridium oxide content and an increased cerium oxide content than the catalytic material prepared in example 1, which contains 50% iridium oxide, while the radical scavenging ability is mainly based on cerium oxide. The catalytic material prepared in example 3 had a relatively low cerium oxide content, and after the Fenton experiment, the fluoride ion release rate was higher than that of the catalytic material in example 1, but lower than that of comparative example 2. Catalytic Material prepared in example 4Since the radical elimination performance of cerium oxide was improved due to the doping of Zr element, the fluorine ion release rate thereof was the lowest among the catalytic materials prepared in examples 1 to 4. Specifically, the order of the fluoride ion release rate is: example 4<Example 2<Example 1<Example 3<Comparative example 2.
It should be understood that the above-mentioned embodiments of the present invention are only examples for clearly illustrating the technical solutions of the present invention, and are not intended to limit the specific embodiments of the present invention. Any modification, equivalent replacement, and improvement made within the spirit and principle of the present invention claims should be included in the protection scope of the present invention claims.
Claims (10)
1. The multifunctional mixed oxide electrocatalytic material consists of metal oxide A with oxygen storing capacity and metal oxide B with oxygen separating reaction catalytic activity.
2. The mixed oxide multifunctional electrocatalytic material of claim 1, wherein said metal oxide a is an oxide of cerium and said metal oxide B is an oxide of iridium and/or ruthenium.
3. The mixed oxide multifunctional electrocatalytic material of claim 1, wherein said metal oxide a is a mixture of one or more of ceria, ceria trioxide, doped ceria and doped ceria; and/or the metal oxide B is one or more of iridium oxide, ruthenium oxide and iridium-ruthenium mixed oxide.
4. The mixed oxide multifunctional electrocatalytic material as set forth in any one of claims 1 to 3, wherein the mass fraction of said metal oxide B in the electrocatalytic material is 20-90%.
5. The mixed oxide multifunctional electrocatalytic material of claim 3, wherein the doping elements in the doped ceria and doped ceria are one or more of transition metal elements or lanthanide metal elements.
6. The mixed oxide multifunctional electrocatalytic material as recited in claim 5, wherein the doping elements in said doped ceria and doped ceria are one or more of Mn, Cu, Ti, Pr, Gd, Zr.
7. The mixed oxide multifunctional electrocatalytic material as claimed in claim 5, wherein the atomic mass of the doping element in the doped ceria and doped ceria is 1-20% of the atomic mass of cerium.
8. A method for preparing the mixed oxide multifunctional electrocatalytic material as claimed in any one of claims 1 to 7, wherein the water-soluble compound containing cerium and/or the water-soluble compound containing cerium and doping element are dissolved, subjected to first hydrothermal reaction, washed and dried; and adding an iridium-containing water-soluble compound or a ruthenium-iridium-containing water-soluble compound, uniformly mixing, carrying out a second hydrothermal reaction, carrying out suction filtration and washing to obtain a precipitate, drying the precipitate, and calcining to obtain the mixed oxide multifunctional electrocatalytic material.
9. The preparation method of the mixed oxide multifunctional electrocatalytic material as set forth in claim 8, comprising the following steps:
s1, dissolving a water-soluble compound containing cerium and/or a water-soluble compound containing cerium and doping elements in water to form a solution, and then mixing the solution and an alkali metal hydroxide aqueous solution with a certain concentration in a polytetrafluoroethylene reaction kettle to form a uniform solution;
s2: placing the reaction kettle in the S1 in an oven, preserving heat for 12-24 hours at 100-180 ℃, washing and filtering a product for 2-5 times by using water and ethanol after the hydrothermal reaction is finished, and then drying the product in the oven for a period of time;
s3: adding the dried product in S2 into an alkali metal hydroxide solution with a certain concentration, uniformly mixing, adding a water-soluble compound containing iridium or a water-soluble compound containing ruthenium and iridium, mixing, and transferring to a polytetrafluoroethylene reaction kettle to form a uniform solution;
s4: and (3) placing the reaction kettle in S3 in an oven, preserving heat for 12-24 h at the temperature of 100-.
10. The mixed oxide multifunctional electrocatalytic material as set forth in any one of claims 1 to 9, wherein said mixed oxide multifunctional electrocatalytic material is used to form a membrane electrode assembly; the membrane electrode assembly can be used as a composition basis of a fuel cell stack.
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