CN113964336A - Anti-reversal catalyst and preparation method and application thereof - Google Patents
Anti-reversal catalyst and preparation method and application thereof Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 80
- 238000002360 preparation method Methods 0.000 title claims abstract description 34
- 229910052741 iridium Inorganic materials 0.000 claims abstract description 54
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 claims abstract description 54
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 49
- 238000000034 method Methods 0.000 claims abstract description 32
- 239000002738 chelating agent Substances 0.000 claims abstract description 28
- 239000000243 solution Substances 0.000 claims abstract description 24
- HTXDPTMKBJXEOW-UHFFFAOYSA-N dioxoiridium Chemical compound O=[Ir]=O HTXDPTMKBJXEOW-UHFFFAOYSA-N 0.000 claims abstract description 22
- 229910000457 iridium oxide Inorganic materials 0.000 claims abstract description 22
- 239000011259 mixed solution Substances 0.000 claims abstract description 21
- 238000010438 heat treatment Methods 0.000 claims abstract description 18
- 239000002243 precursor Substances 0.000 claims abstract description 15
- 238000002156 mixing Methods 0.000 claims abstract description 5
- 239000000203 mixture Substances 0.000 claims abstract description 3
- 238000006722 reduction reaction Methods 0.000 claims description 21
- 239000000446 fuel Substances 0.000 claims description 16
- 239000002253 acid Substances 0.000 claims description 15
- 238000003756 stirring Methods 0.000 claims description 14
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 13
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- 238000006243 chemical reaction Methods 0.000 claims description 10
- 238000005406 washing Methods 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 8
- 230000002572 peristaltic effect Effects 0.000 claims description 8
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 claims description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 3
- KZLHPYLCKHJIMM-UHFFFAOYSA-K iridium(3+);triacetate Chemical compound [Ir+3].CC([O-])=O.CC([O-])=O.CC([O-])=O KZLHPYLCKHJIMM-UHFFFAOYSA-K 0.000 claims description 3
- 238000005119 centrifugation Methods 0.000 claims description 2
- DANYXEHCMQHDNX-UHFFFAOYSA-K trichloroiridium Chemical compound Cl[Ir](Cl)Cl DANYXEHCMQHDNX-UHFFFAOYSA-K 0.000 claims description 2
- 230000002776 aggregation Effects 0.000 abstract description 29
- 238000005054 agglomeration Methods 0.000 abstract description 28
- 239000002923 metal particle Substances 0.000 abstract description 26
- 230000003197 catalytic effect Effects 0.000 abstract description 13
- 238000000197 pyrolysis Methods 0.000 abstract description 9
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 abstract description 8
- 229910000510 noble metal Inorganic materials 0.000 abstract description 7
- 239000003381 stabilizer Substances 0.000 abstract description 5
- 230000000052 comparative effect Effects 0.000 description 21
- 239000000047 product Substances 0.000 description 10
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 9
- 229910052799 carbon Inorganic materials 0.000 description 9
- 239000002245 particle Substances 0.000 description 9
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 8
- 239000001301 oxygen Substances 0.000 description 7
- 229910052760 oxygen Inorganic materials 0.000 description 7
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 6
- 230000007797 corrosion Effects 0.000 description 6
- 238000005260 corrosion Methods 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 238000006479 redox reaction Methods 0.000 description 6
- 238000001816 cooling Methods 0.000 description 5
- 230000002829 reductive effect Effects 0.000 description 5
- 238000003917 TEM image Methods 0.000 description 4
- 239000007795 chemical reaction product Substances 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 230000007935 neutral effect Effects 0.000 description 4
- 239000001509 sodium citrate Substances 0.000 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 description 4
- 239000004408 titanium dioxide Substances 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
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- 238000005868 electrolysis reaction Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 230000010287 polarization Effects 0.000 description 3
- 239000003575 carbonaceous material Substances 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 239000003273 ketjen black Substances 0.000 description 2
- 230000033001 locomotion Effects 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 229910052758 niobium Inorganic materials 0.000 description 2
- 239000010955 niobium Substances 0.000 description 2
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 230000002441 reversible effect Effects 0.000 description 2
- 229910001415 sodium ion Inorganic materials 0.000 description 2
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 229920000557 Nafion® Polymers 0.000 description 1
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- 239000003792 electrolyte Substances 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 239000011943 nanocatalyst Substances 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
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- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
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- 239000004317 sodium nitrate Substances 0.000 description 1
- 235000010344 sodium nitrate Nutrition 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
- H01M4/92—Metals of platinum group
- H01M4/921—Alloys or mixtures with metallic elements
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/88—Processes of manufacture
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
- H01M4/92—Metals of platinum group
- H01M4/923—Compounds thereof with non-metallic elements
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
- H01M4/92—Metals of platinum group
- H01M4/925—Metals of platinum group supported on carriers, e.g. powder carriers
- H01M4/926—Metals of platinum group supported on carriers, e.g. powder carriers on carbon or graphite
-
- 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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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Catalysts (AREA)
Abstract
The invention provides a reverse-polarity-resistant catalyst, a preparation method and application thereof, wherein the reverse-polarity-resistant catalyst is a mixture of iridium and iridium oxide, and the preparation method comprises the following steps: (1) mixing an iridium precursor, a chelating agent and an ethylene glycol solution to obtain a mixed solution; (2) heating and reducing the mixed solution obtained in the step (1) in a microwave reactor to obtain the anti-antipole catalyst; wherein the ethylene glycol solution is alkaline, and the mass ratio of the chelating agent to the iridium precursor is more than 1. The iridium oxide antipole catalyst is prepared by continuous microwave assistance, product difference caused by different batches of preparation is avoided, the chelating agent is used as the stabilizer, the agglomeration difficulty of iridium metal particles is increased, the agglomeration of the iridium metal particles is avoided, meanwhile, the preparation method adopts a glycol reduction method, the high-temperature treatment process is also avoided, the agglomeration growth of the metal particles caused by high-temperature pyrolysis is further avoided, and the utilization rate and the catalytic activity of the noble metal iridium are improved.
Description
Technical Field
The invention belongs to the technical field of catalyst preparation, relates to an anti-reversal catalyst, a preparation method and application thereof, and particularly relates to an iridium-containing anti-reversal catalyst used in a fuel cell, and a preparation method and application thereof.
Background
The hydrogen-oxygen fuel cell focuses on the attention of a plurality of enterprises with the advantages of high conversion rate, high power density, zero emission and the like. Although it is called a battery, it is different from the traditional energy storage battery, it should be called a power generation device strictly, and the chemical energy of hydrogen and oxygen is converted into electric energy through chemical reaction, so the fuel cell has been used in the fields of power cars, small and medium power stations, communication base stations, aerospace craft, etc.
As a power source, the service life of a fuel cell is one of the keys whether the fuel cell can be used in a large number of commercial applications, and there are many key factors that affect the service life, such as water heat management, gas distribution, component corrosion, and the like. Wherein the gas distribution is uneven, which causes the gas supply of the battery body to be insufficient, and the voltage of the single battery is caused to be sharply attenuated and even become negative, namely, the reverse pole phenomenon occurs. This phenomenon is likely to occur in complex operating conditions such as start-stop, idle, high power operation, and rapid and frequent load and unload. When the anode is reversed, electrolysis of water and corrosion of carbon occur to provide sufficient electrons and protons in order to maintain the overall reaction. The carbon corrosion is irreversible, the carbon material is mainly a carrier of the catalyst at the anode, and the catalytic active metal Pt loaded on the surface of the carbon material can be agglomerated and fall off along with the corrosion of the carbon, so that the catalytic layer is damaged, the activity is reduced, and the heat generated by the serious antipole phenomenon can cause perforation of the proton exchange membrane, short circuit of the anode and the cathode, fuel intermixing and other serious consequences.
In order to reduce the harm of the reverse-pole phenomenon to the fuel cell, two aspects can be considered: system control strategy Regulation H2The supply of (2) and the addition of a counter-electrode-resistant catalyst to the anode reduce the occurrence of carbon corrosion. Wherein, for the antipole catalyst, the main function is to promote the electrolysis of water and strictly speaking to promote the oxygen evolution reaction, because the electrolysis atmosphere of water is hydrogen evolution reaction and oxygen evolution reaction, and compared with the hydrogen evolution reaction, the oxygen evolution reaction is oppositeThe process should be slower.
At present, the commercial antipole catalyst is mainly iridium and iridium oxide, but iridium is used as a noble metal, the expensive cost of iridium severely limits the commercial use of iridium, and therefore, the catalytic activity of the catalyst must be improved to reduce the use amount of iridium. However, the currently common preparation method of iridium oxide is an air pyrolysis method, and agglomeration and growth of iridium oxide are easily caused in a high-temperature oxidation process, so that the particle size is large, the utilization rate is low, and the activity is low.
CN111029599A discloses a fuel cell anti-reversal catalyst and a preparation method thereof, wherein the catalyst comprises an iridium oxide and niobium composite doped titanium dioxide nano catalyst. Wherein the niobium doped titanium dioxide is the support. By the method, the catalyst can effectively relieve carbon carrier corrosion and platinum particle agglomeration growth when anode side of the fuel cell is subjected to reversal, so that the reversal resistant time of the fuel cell is prolonged. However, in the patent, the niobium-doped titanium dioxide is used as a carrier, the preparation process is complex, the catalyst with high metal loading rate (more than or equal to 30 wt%) is difficult to obtain, and the niobium-doped titanium dioxide has low conductivity and is not beneficial to the occurrence of electrochemical reaction.
CN112151811A discloses a catalyst composite for a fuel cell and a method for manufacturing the same, the catalyst composite comprising a support comprising carbon (C), platinum (Pt) supported on the support, and iridium (Ir) compound supported on the support. In this way, the invention can stably control the voltage reversal, increase the life of the fuel cell stack, and also can achieve cost reduction by reducing replacement cost. However, during the preparation of the patent, the pH value of the solution is adjusted by adding NaOH and HCl, so that Na ion and Cl ion impurities are remained in the product, the concentration of the Na ion and the Cl ion cannot be reduced to the required level by washing and filtering, and the two impurity ions can cause non-negligible influence on the service life of key parts of the fuel cell; and the formation process of the iridium oxide particles is finished at about 200 ℃ to 400 ℃ in the air, so that not only the carbon carrier can be decomposed, but also the obtained iridium oxide particles are dispersed unevenly under the high-temperature condition, the agglomeration phenomenon is generated, the performance of the catalyst is influenced, and the service life of the fuel cell stack is shortened.
Therefore, how to reduce the agglomeration of active particles and improve the catalytic activity of the iridium-containing anti-reversal catalyst in the process of preparing the iridium-containing anti-reversal catalyst is a technical problem to be solved urgently.
Disclosure of Invention
The invention aims to provide an anti-reversal catalyst, a preparation method and application thereof. The iridium oxide antipole catalyst is prepared by continuous microwave assistance, product difference caused by different batches of preparation is avoided, the chelating agent is used as the stabilizer, the agglomeration difficulty of iridium metal particles is increased, the agglomeration of the iridium metal particles is avoided, meanwhile, the preparation method adopts a glycol reduction method, the high-temperature treatment process is also avoided, the agglomeration growth of the metal particles caused by high-temperature pyrolysis is further avoided, and the utilization rate and the catalytic activity of the noble metal iridium are improved.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the present invention provides a preparation method of a counter-electrode-resistant catalyst, comprising the steps of:
(1) mixing an iridium precursor, a chelating agent and an ethylene glycol solution to obtain a mixed solution;
(2) heating and reducing the mixed solution obtained in the step (1) in a microwave reactor to obtain the anti-antipole catalyst;
wherein the glycol solution is alkaline, and the mass ratio of the chelating agent to the iridium precursor is more than 1, for example, the mass ratio may be 1.5, 2, 2.5, 3, 4 or 5.
The iridium oxide antipole catalyst is prepared by continuous microwave assistance, product difference caused by different batches of preparation is avoided, the chelating agent is used as the stabilizer, the agglomeration difficulty of iridium metal particles is increased, the agglomeration of the iridium metal particles is avoided, meanwhile, the preparation method adopts a glycol reduction method, the high-temperature treatment process is also avoided, the agglomeration growth of the metal particles caused by high-temperature pyrolysis is further avoided, and the utilization rate and the catalytic activity of the noble metal iridium are improved.
According to the invention, a glycol reduction method is adopted, and a chelating agent is matched at the same time, so that the chelating agent and iridium metal ions have a chelating effect, the agglomeration difficulty of iridium metal particles is increased, the agglomeration of iridium metal particles is avoided, and meanwhile, the glycol reduction method does not need high-temperature treatment, further avoids the particle agglomeration of iridium metal particles caused by high-temperature pyrolysis, and finally improves the utilization rate and catalytic activity of noble metal iridium;
in the invention, if no chelating agent is added or the addition amount is too small, the reduced metal particles can agglomerate and grow, and the exposure amount of active crystal faces and the catalytic efficiency are reduced.
In the invention, the microwave reactor is adopted, so that the continuous preparation of the product can be realized, and the anti-antipole catalyst does not need to be prepared in batches, thereby avoiding the difference of the product caused by different batches of preparation, improving the uniformity of the anti-antipole catalyst product in the invention and improving the utilization rate of the anti-antipole catalyst product.
Preferably, the iridium precursor in step (1) includes any one of chloroiridic acid, iridium acetate or iridium chloride or a combination of at least two of them.
Preferably, the chelating agent of step (1) comprises citric acid and/or a citrate.
In the present invention, citric acid or citrate is used as a chelating agent, and an effect of inhibiting the aggregation of metal particles can be achieved.
Preferably, the mass ratio of the chelating agent to the iridium precursor in the step (1) is (1.5-4): 1, for example, 1.5:1, 2:1, 2.5:1, 3:1, 3.5:1 or 4: 1.
Preferably, the pH value of the mixed solution in the step (1) is 12-14, such as 12, 13 or 14.
According to the invention, the pH value of the mixed solution is ensured to be within the range of 12-14, and the reduction of the metal precursor is facilitated.
Preferably, in step (2), the flow rate of the peristaltic pump in the microwave reactor is 30-150 mL/min, such as 30mL/min, 40mL/min, 50mL/min, 60mL/min, 70mL/min, 80mL/min, 90mL/min, 100mL/min, 110mL/min, 120mL/min, 130mL/min, 140mL/min, 150mL/min, or the like.
Preferably, the temperature of the heating reduction reaction in the step (2) is 150 to 180 ℃, for example, 150 ℃, 155 ℃, 160 ℃, 165 ℃, 170 ℃, 175 ℃ or 180 ℃.
In the invention, the over-high temperature of heating reduction can cause the enhancement of the thermal motion of metal particles and increase the agglomeration probability of the metal particles, while the over-low temperature is not beneficial to the reduction reaction or even does not react.
Preferably, in the step (2), an acid is added to the solution after the heating reduction reaction, and the pH is adjusted to 2 to 4, for example, 2, 3, or 4.
In the invention, acid is added after the heating reduction reaction, so that the chelating agent chelated with the iridium metal ions can be removed, the iridium-based metal particles are fully exposed, and the utilization rate of the metal particles is improved.
Preferably, the acid comprises dilute hydrochloric acid and/or dilute sulfuric acid.
Preferably, after the addition of the acid, stirring, centrifugation, water washing and drying are sequentially performed.
As a preferred technical scheme, the preparation method comprises the following steps:
(1) mixing an iridium precursor, a chelating agent and an ethylene glycol solution to obtain a mixed solution with the pH value of 12-14;
(2) heating and reducing the mixed solution obtained in the step (1) in a microwave reactor at a temperature of 150-180 ℃ at a peristaltic pump flow of 30-150 mL/min, adding an acid to adjust the pH value to 2-4 after reaction, and sequentially stirring, centrifuging, washing and drying to obtain the anti-reversal catalyst;
wherein the mass ratio of the chelating agent to the iridium precursor is (1.5-4) to 1.
In a second aspect, the present invention provides a reverse-polarity-resistant catalyst prepared by the method for preparing a reverse-polarity-resistant catalyst according to the first aspect; the anti-reversal catalyst is a mixture of iridium and iridium oxide.
In a third aspect, the present invention also provides a use of the anti-reversal catalyst according to the second aspect in a fuel cell.
Compared with the prior art, the invention has the following beneficial effects:
the iridium oxide anti-reversal catalyst is prepared by continuous microwave assistance, the product difference caused by different batches of preparation is avoided, the chelating agent is used as the stabilizer, the agglomeration difficulty of iridium metal particles is increased, the agglomeration of the iridium metal particles is avoided, meanwhile, the preparation method by the ethylene glycol reduction method also avoids the high-temperature treatment process, the agglomeration and growth of the metal particles caused by high-temperature pyrolysis are further avoided, the utilization rate and the catalytic activity of noble metal iridium are improved, and the anti-reversal catalyst is enabled to be at 10mA-2The overpotential of the oxidation-reduction reaction is as low as 305mV, and the overpotential of the oxidation-reduction reaction can be made to be lower than 297mV by further regulating the temperature of the oxidation-reduction reaction.
Drawings
Figure 1 is a TEM image of the catalyst provided in example 1.
Fig. 2 is a TEM image of the catalyst provided in comparative example 1.
Fig. 3 is a comparative plot of the polarization curves of the catalysts provided in example 1, comparative example 1 and comparative example 2.
Detailed Description
The technical solution of the present invention is further explained by the following embodiments. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.
Example 1
This example provides a preparation method of an anti-reversal catalyst, which comprises the following steps:
dissolving 10mg of chloroiridic acid and 25mg of sodium citrate in an alkaline ethylene glycol solution, and continuously stirring until the solution is clear and the pH value of the mixed solution is 12;
and then setting the flow rate of a peristaltic pump to be 50mL/min, transferring the mixed solution into a microwave reactor, adjusting the heating temperature of the microwave reactor to 160 ℃ for reduction reaction, allowing the reaction product to flow out of the microwave reactor, cooling to room temperature, adding dilute sulfuric acid, adjusting the pH to 3, stirring for 4 hours, centrifugally collecting, washing with deionized water to be neutral, transferring into an oven, and drying at 60 ℃ to obtain the final iridium/iridium oxide catalyst.
Figure 1 shows a TEM image of an iridium/iridium oxide catalyst supported on a carbon support as provided in example 1, from which it can be seen that the catalyst particles are uniformly distributed without significant agglomeration.
Example 2
Dissolving 10mg of chloroiridic acid and 25mg of sodium citrate in an alkaline ethylene glycol solution, and continuously stirring until the solution is clear and the pH value of the mixed solution is 12;
and setting the flow rate of a peristaltic pump to be 100mL/min, transferring the mixed solution into a microwave reactor, adjusting the heating temperature of the microwave reactor to 180 ℃ for reduction reaction, allowing the reaction product to flow out of the microwave reactor, cooling to room temperature, adding dilute sulfuric acid, adjusting the pH to 3, stirring for 4 hours, centrifugally collecting, washing with deionized water to be neutral, transferring into an oven, and drying at 60 ℃ to obtain the final iridium/iridium oxide catalyst.
Example 3
Dissolving 10mg of iridium acetate and 15mg of citric acid in an alkaline glycol solution, and continuously stirring until the solution is clear and the pH value of the mixed solution is 14;
and then setting the flow rate of a peristaltic pump to be 140mL/min, transferring the mixed solution into a microwave reactor, adjusting the heating temperature of the microwave reactor to 150 ℃ for reduction reaction, allowing the reaction product to flow out of the microwave reactor, cooling to room temperature, adding dilute sulfuric acid, adjusting the pH to 4, stirring for 5 hours, centrifugally collecting, washing with deionized water to be neutral, transferring into an oven, and drying at 60 ℃ to obtain the final iridium/iridium oxide catalyst.
Example 4
Dissolving 10mg of chloroiridic acid and 40mg of sodium citrate in an alkaline ethylene glycol solution, and continuously stirring until the solution is clear and the pH value of the mixed solution is 13;
and then setting the flow rate of a peristaltic pump to be 30mL/min, transferring the mixed solution into a microwave reactor, adjusting the heating temperature of the microwave reactor to 160 ℃ for reduction reaction, allowing the reaction product to flow out of the microwave reactor, cooling to room temperature, adding dilute sulfuric acid, adjusting the pH to 2, stirring for 3 hours, centrifugally collecting, washing with deionized water to be neutral, transferring into an oven, and drying at 80 ℃ to obtain the final iridium/iridium oxide catalyst.
Example 5
This example differs from example 1 in that the temperature of the reduction reaction in this example was 200 ℃.
The remaining preparation methods and parameters were in accordance with example 1.
Comparative example 1
The comparative example differs from example 1 in that the chelating agent sodium citrate was not added.
The remaining preparation methods and parameters were in accordance with example 1.
Fig. 1 and 2 show TEM images of example 1 and comparative example 1 dispersed in a ketjen black carbon support, respectively, and it can be seen from comparison between fig. 1 and 2 that agglomeration of catalyst particles is more significant in comparative example 1, which further affects the catalytic activity of the anti-reversal catalyst.
Comparative example 2
This comparative example provides a method of preparing a counter-electrode resistant catalyst, the method comprising the steps of:
dissolving 10mg of chloroiridic acid and 70mg of sodium nitrate in water according to the traditional process, continuously stirring until the solution is clear, and heating to 80 ℃ while continuously stirring until the solvent is almost completely removed; and transferring the product to a muffle furnace, carrying out heat treatment at the temperature of 500 ℃ for 1h, cooling to room temperature, and washing in a water-alcohol solution to obtain the final iridium oxide catalyst.
The anti-reversal catalysts provided in examples 1-5 and comparative examples 1-2 were electrochemically tested by the following specific methods:
testing a half cell: the antipole catalysts provided in examples 1 to 5 and comparative examples 1 to 2 (the catalysts provided in examples 1 to 5 and comparative examples 1 to 2 were dispersed in Ketjen black EC-300J first), Nafion (5 wt%) and a solvent were ultrasonically mixed, and 15. mu.L of the dispersed solution was dropped to an area of 0.19625cm-2The surface of the gold electrode is dried at room temperature and then used as a working electrode. Using electrochemical stations at three locationsIn the polar electrolytic cell, a platinum wire was used as a counter electrode, a reversible hydrogen electrode was used as a reference electrode, and a 0.5M nitrogen-saturated sulfuric acid solution was used as an electrolyte, and a polarization curve test was performed at 1600rpm at a sweep rate of 5mV/s, and the results are shown in Table 1.
The polarization curves of the example 1, the comparative example 1 and the comparative example 2 are shown in fig. 3, and it can be seen from the figure that the activity of the anti-reversal catalyst of the example 1 is better than that of the anti-reversal catalysts provided by the comparative example 1 and the comparative example 2, which shows that the addition of the chelating agent well hinders the agglomeration of catalyst particles and well improves the activity of the finally obtained iridium/iridium oxide catalyst; compared with the traditional high-temperature pyrolysis method, the method provided by the invention has smaller initial potential and overpotential (10mA cm)-2) Therefore, the catalyst has better capability of catalyzing oxygen evolution and anti-extreme capability.
TABLE 1
| Overpotential (mV) @10mA.cm-2 | |
| Example 1 | 285 |
| Example 2 | 297 |
| Example 3 | 295 |
| Example 4 | 287 |
| Example 5 | 305 |
| Comparative example 1 | 310 |
| Comparative example 2 | 315 |
From the data results of example 1 and example 5, it is understood that when the heating reduction temperature is too high, the thermal movement of the metal particles is enhanced, the agglomeration phenomenon is likely to occur, and the catalytic activity and the utilization rate of the catalyst are reduced.
As can be seen from the data results of example 1 and comparative example 1, the overpotential significantly increases during the preparation of the anti-reversal catalyst without adding the chelating agent, which is probably due to the large amount of agglomeration of the metal particles caused by the absence of the chelating agent.
As can be seen from the data results of example 1 and comparative example 2, the preparation method proposed by the present invention has smaller initial potential and overpotential (10mA cm) compared with the conventional high temperature pyrolysis method, without adding an additional oxidant to prepare the catalyst-2) Therefore, the catalyst has better capability of catalyzing oxygen evolution and anti-extreme capability.
In conclusion, the iridium oxide anti-reversal catalyst is prepared by continuous microwave assistance, the product difference caused by different batches of preparation is avoided, the chelating agent is used as the stabilizer, the agglomeration difficulty of iridium metal particles is increased, the agglomeration of iridium metal particles is avoided, meanwhile, the iridium oxide anti-reversal catalyst is prepared by a glycol reduction method, the high-temperature treatment process is also avoided, the agglomeration growth of metal particles caused by high-temperature pyrolysis is further avoided, the utilization rate and the catalytic activity of noble metal iridium are improved, and the anti-reversal catalyst is enabled to be at 10mA-2The overpotential of the oxidation-reduction reaction is as low as 305mV, and the overpotential of the oxidation-reduction reaction can be made to be lower than 297mV by further regulating the temperature of the oxidation-reduction reaction.
The applicant declares that the above description is only a specific embodiment of the present invention, but the scope of the present invention is not limited thereto, and it should be understood by those skilled in the art that any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are within the scope and disclosure of the present invention.
Claims (10)
1. A preparation method of a counter-electrode resistant catalyst is characterized by comprising the following steps:
(1) mixing an iridium precursor, a chelating agent and an ethylene glycol solution to obtain a mixed solution;
(2) heating and reducing the mixed solution obtained in the step (1) in a microwave reactor to obtain the anti-antipole catalyst;
wherein the ethylene glycol solution is alkaline, and the mass ratio of the chelating agent to the iridium precursor is more than 1.
2. The method of preparing a antipole catalyst according to claim 1, wherein the iridium precursor of step (1) includes any one of or a combination of at least two of chloroiridic acid, iridium acetate, or iridium chloride;
preferably, the chelating agent of step (1) comprises citric acid and/or a citrate.
3. The preparation method of the anti-reversal catalyst according to claim 1 or 2, characterized in that the mass ratio of the chelating agent to the iridium precursor in the step (1) is (1.5-4): 1.
4. The method for preparing a antipole catalyst according to any one of claims 1 to 3, wherein the pH of the mixed solution in the step (1) is 12 to 14.
5. The method for preparing the anti-reversal catalyst according to any one of claims 1 to 4, wherein in the step (2), the flow rate of a peristaltic pump in the microwave reactor is 30 to 150 mL/min;
preferably, the temperature of the heating reduction reaction in the step (2) is 150-180 ℃.
6. The preparation method of the anti-reversal catalyst according to any one of claims 1 to 5, characterized in that in the step (2), an acid is added to the solution after the heating reduction reaction, and the pH value is adjusted to 2-4;
preferably, the acid comprises dilute hydrochloric acid and/or dilute sulfuric acid.
7. The method of claim 6, wherein the acid is added, and the stirring, the centrifugation, the water washing and the drying are sequentially performed.
8. The method for preparing a catalyst resistant to reverse-polarization according to any one of claims 1 to 7, comprising the steps of:
(1) mixing an iridium precursor, a chelating agent and an ethylene glycol solution to obtain a mixed solution with the pH value of 12-14;
(2) heating and reducing the mixed solution obtained in the step (1) in a microwave reactor at a temperature of 150-180 ℃ at a peristaltic pump flow of 30-150 mL/min, adding an acid to adjust the pH value to 2-4 after reaction, and sequentially stirring, centrifuging, washing and drying to obtain the anti-reversal catalyst;
wherein the mass ratio of the chelating agent to the iridium precursor is (1.5-4) to 1.
9. An anti-reversal catalyst, characterized in that the anti-reversal catalyst is prepared by the preparation method of the anti-reversal catalyst according to any one of claims 1 to 8; the anti-reversal catalyst is a mixture of iridium and iridium oxide.
10. Use of a reverse-polarity-resistant catalyst according to claim 9 for a fuel cell.
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