CN114164458B - Preparation method of iridium-ruthenium-based oxygen evolution catalyst - Google Patents

Preparation method of iridium-ruthenium-based oxygen evolution catalyst Download PDF

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CN114164458B
CN114164458B CN202111264578.4A CN202111264578A CN114164458B CN 114164458 B CN114164458 B CN 114164458B CN 202111264578 A CN202111264578 A CN 202111264578A CN 114164458 B CN114164458 B CN 114164458B
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iridium
ruthenium
precursor
oxygen evolution
based oxygen
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CN114164458A (en
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任航星
李黎明
宋时莉
袁先明
焦文强
孙岳涛
李朋喜
王杰鹏
杨金彭
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718th Research Institute of CSIC
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    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
    • C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
    • C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
    • C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
    • C25B11/091—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of at least one catalytic element and at least one catalytic compound; consisting of two or more catalytic elements or catalytic compounds
    • C25B11/093—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of at least one catalytic element and at least one catalytic compound; consisting of two or more catalytic elements or catalytic compounds at least one noble metal or noble metal oxide and at least one non-noble metal oxide
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B1/00—Electrolytic production of inorganic compounds or non-metals
    • C25B1/01—Products
    • C25B1/02—Hydrogen or oxygen
    • C25B1/04—Hydrogen or oxygen by electrolysis of water
    • 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
    • Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis

Abstract

The embodiment of the invention discloses a preparation method of an iridium ruthenium based oxygen evolution catalyst, which comprises the steps of dissolving an iridium precursor and a ruthenium precursor in a solvent to obtain a mixed solution; adding a pore-forming agent and sodium nitrate into the mixed solution, heating, roasting and washing to obtain an iridium ruthenium oxide crude product, carrying out pre-leaching treatment on the iridium ruthenium oxide crude product by using an acid solution, washing and drying to obtain the iridium ruthenium based oxygen evolution catalyst. The catalyst with low iridium loading capacity, high efficiency and high reliability prepared by the preparation method is beneficial to solving the technical problem of overhigh cost caused by high iridium element content of the iridium catalyst in the prior art.

Description

Preparation method of iridium-ruthenium-based oxygen evolution catalyst
Technical Field
The invention relates to a preparation method of a catalyst, in particular to a preparation method of an iridium ruthenium based oxygen evolution catalyst.
Background
Electro-hydrogen is a popular energy carrier and is considered as a key element of future sustainable energy systems. At present, hydrogen economy based on large-scale water electrolysis is rapidly evolving, i.e. hydrogen is obtained by electrolysis of water. When electrical energy from renewable energy sources such as photovoltaic, wind, hydroelectric, etc. is used for electrolysis, the green hydrogen produced may not even emit greenhouse gases. At present, there are three main ways for green hydrogen production technology (i.e. water electrolysis technology): proton Exchange Membrane Water Electrolysis (PEMWE) and Alkaline Water Electrolysis (AWE) in the low temperature range, and Solid Oxide Electrolysis (SOEC) in the high temperature range.
PEMWE are considered to be the most promising technology for future large-scale hydrogen production due to their broad current density operating range, i.e., high operating flexibility, rapid dynamic response, and possibility of operating at significant pressure differentials. In PEM water electrolysers, iridium is industrially used as the catalyst for anodic oxygen evolution reactions and platinum-based catalysts for cathodic hydrogen evolution reactions due to its high activity and high stability. Iridium, a Platinum Group Metal (PGM), is one of the most scarce elements on earth, which also results in relatively expensive catalysts, and the global demand for iridium has fluctuated greatly in the past decade, with an increasing trend. To achieve rapid industrialization and future large-scale application of PEMWE, two necessary prerequisites need to be considered to meet future huge iridium requirements: first, the iridium catalyst loading in PEM electrolyzers is greatly reduced, and second, its high efficiency and stability in use is still maintained.
The technical problem that the iridium catalyst in the prior art has high iridium element content and causes high cost is solved.
Disclosure of Invention
In view of the above problems in the prior art, embodiments of the present invention provide a preparation method of an iridium ruthenium based oxygen evolution catalyst, and the preparation method is used to prepare a catalyst with low iridium loading, high efficiency and high reliability, which is helpful for solving the technical problem of high iridium element content and high cost of the iridium catalyst in the prior art.
In an embodiment, an embodiment of the present invention provides a method for preparing an iridium ruthenium based oxygen evolution catalyst, including:
dissolving an iridium precursor and a ruthenium precursor in a solvent to obtain a mixed solution;
adding a pore-forming agent and sodium nitrate into the mixed solution, heating, and roasting and washing to obtain an iridium ruthenium oxide crude product;
and carrying out pre-leaching treatment on the iridium ruthenium oxide crude product by using an acid solution, and washing and drying to obtain the iridium ruthenium based oxygen evolution catalyst.
In one embodiment, the dissolving the iridium precursor and the ruthenium precursor in the solvent to obtain the mixed solution includes:
respectively adding an iridium precursor and a ruthenium precursor into a solvent to obtain an iridium precursor solution and a ruthenium precursor solution;
and dropwise adding the iridium precursor solution into the ruthenium precursor solution to obtain a mixed solution.
In an embodiment, the adding a pore-forming agent and sodium nitrate into the mixed solution, and performing calcination washing after heating to obtain the iridium ruthenium oxide crude product comprises:
adding a pore-forming agent and sodium nitrate into the mixed solution in sequence;
mixing and heating at a first preset temperature to dry the solvent to obtain dry salt;
putting the dry salt into a sintering furnace for roasting to obtain a molten salt-oxide mixture, and cooling to a second preset temperature in the furnace;
washing the cooled molten salt-oxide mixture by deionized water to obtain an oxide;
and drying the washed oxide at a third preset temperature to obtain an iridium ruthenium oxide crude product.
In one embodiment, the pre-leaching treatment of the crude iridium ruthenium oxide product with an acid solution, and washing and drying to obtain the iridium ruthenium based oxygen evolution catalyst comprises:
pre-leaching impurities in the iridium ruthenium oxide crude product by using an acid solution to obtain a solid product;
washing the solid product by the deionized water until the pH value is neutral;
and drying the washed solid product at a fourth preset temperature to obtain the iridium ruthenium based oxygen evolution catalyst.
In one embodiment, the iridium precursor solution is added dropwise to the ruthenium precursor solution at a dropping rate of 1 to 15mL/min, wherein the metal concentration in the iridium precursor solution and the ruthenium precursor solution is 0.05 to 0.5mol/L.
In one embodiment, the mass ratio of the sodium nitrate to the metal precursor in the mixed solution is 5 to 30:1.
in one embodiment, the baking temperature is 350 to 550 ℃, the heating rate is 2 to 10 ℃/min, and the baking time is 0.5 to 3 hours.
In one embodiment, the molar ratio of the pore-forming agent to the metal of the mixed solution is 10 to 200:1, the reaction time of the pore-forming agent and the metal precursor in the mixed solution is 0.5 to 3 hours.
In one embodiment, the temperature of the pre-leaching is 60 to 120 degrees celsius and the pre-leaching time is 0.5 to 6 hours.
In one embodiment, the acid solution has an acid concentration of 0.05 to 2mol/L.
Drawings
FIG. 1 is a schematic flow diagram 100 illustrating a process for producing an iridium ruthenium based oxygen evolution catalyst in one embodiment of the present invention;
FIG. 2 is a schematic flow diagram 200 illustrating a process for producing an iridium ruthenium based oxygen evolution catalyst in another embodiment of the present invention;
FIG. 3 is a schematic flow diagram 300 illustrating a process for producing an iridium ruthenium based oxygen evolution catalyst in another embodiment of the present invention;
FIG. 4 is a schematic flow diagram 400 illustrating a process for producing an iridium ruthenium based oxygen evolution catalyst in another embodiment of the present invention;
FIG. 5 is a SEM-EDS schematic of iridium ruthenium oxide produced in an example of the present invention;
FIG. 6 is a N2 adsorption/desorption curve for oxygen evolution catalysts of example 1 and comparative example 3 of the present invention;
FIG. 7 is a linear sweep voltammogram of oxygen evolution catalysts of example 1 and comparative example 3 of the present invention;
FIG. 8 is a linear sweep voltammogram before and after the stability test of the oxygen evolution catalyst of example 1 of the present invention;
FIG. 9 is a plot of current density versus voltage for example 1 of the invention and comparative example 3 tested in a proton exchange membrane electrolyzer.
Detailed Description
In order to make the technical solutions of the present invention better understood, the present invention will be described in detail below with reference to the accompanying drawings and specific embodiments.
Various aspects and features of the present application are described herein with reference to the drawings.
These and other characteristics of the present application will become apparent from the following description of a preferred form of embodiment, given as a non-limiting example, with reference to the attached drawings.
It should also be understood that, although the present application has been described with reference to some specific examples, a person of skill in the art shall certainly be able to achieve many other equivalent forms of application, having the characteristics as set forth in the claims and hence all coming within the field of protection defined thereby.
The above and other aspects, features and advantages of the present application will become more apparent in view of the following detailed description when taken in conjunction with the accompanying drawings.
Specific embodiments of the present application are described hereinafter with reference to the accompanying drawings; however, it is to be understood that the disclosed embodiments are merely exemplary of the application, which can be embodied in various forms. Well-known and/or repeated functions and structures have not been described in detail so as to not unnecessarily obscure the present application with unnecessary or unnecessary detail. Therefore, specific structural and functional details disclosed herein are not to be interpreted as limiting, but merely as a basis for the claims and as a representative basis for teaching one skilled in the art to variously employ the present application in virtually any appropriately detailed structure.
The specification may use the phrases "in one embodiment," "in another embodiment," "in yet another embodiment," or "in other embodiments," which may each refer to one or more of the same or different embodiments in accordance with the application.
FIG. 1 is a schematic flow diagram 100 illustrating a process for preparing an iridium ruthenium based oxygen evolution catalyst in an embodiment of the present invention. As shown in fig. 1, in one embodiment, the present application provides a method of preparing an iridium ruthenium based oxygen evolution catalyst, the method comprising:
s101, dissolving an iridium precursor and a ruthenium precursor in a solvent to obtain a mixed solution.
In this step, a specific step of dissolving an iridium precursor and a ruthenium precursor into a solvent is provided. In this step, the iridium precursor and the ruthenium precursor are completely dissolved in the solvent by stirring with a stirring device and the mixed solution is obtained. Wherein the iridium precursor is one or more of iridium tetrachloride, iridium trichloride, chloroiridic acid, iridium acetate, ammonium chloroiridate, potassium chloroiridate and sodium chloroiridate. The ruthenium precursor is one or more of ruthenium trichloride, ammonium chlororuthenate, potassium chlororuthenate and sodium chlororuthenate. The solvent is one or more of methanol, ethanol, n-propanol, isopropanol, ethylene glycol and water.
And S102, adding a pore-forming agent and sodium nitrate into the mixed solution, heating, and roasting and washing to obtain a crude iridium ruthenium oxide product.
In the step, a specific step of adding the pore-forming agent and the sodium nitrate into the mixed solution and carrying out subsequent treatment to obtain the iridium ruthenium oxide crude product is provided. The pore-forming agent is one or more of ammonium carbonate, ammonium bicarbonate, ammonium chloride, ammonia water, carbon powder, polyvinyl alcohol, urea, methyl methacrylate, polyvinyl chloride and polystyrene.
S103, carrying out pre-leaching treatment on the iridium ruthenium oxide crude product by using an acid solution, and washing and drying to obtain the iridium ruthenium based oxygen evolution catalyst.
The specific step is provided for carrying out pre-leaching treatment on the iridium ruthenium oxide crude product, carrying out acid-base equilibrium and drying to finally obtain the iridium ruthenium based oxygen evolution catalyst.
A specific preparation method of the iridium ruthenium based oxygen evolution catalyst is provided in this example. The chemical general formula of the iridium ruthenium-based oxygen evolution catalyst is Ir x Ru y O 2 Wherein x is more than or equal to 0.3 and less than or equal to 0.8,0.2 and less than or equal to 0.7, and x + y =1; the iridium ruthenium based oxygen evolution catalyst can be applied to PEM electrolyzed water, regenerative fuel cells and fuel cell anti-reversal additives.
In addition, the iridium and ruthenium metal precursor solution is mixed to dope ruthenium into iridium to prepare the iridium-ruthenium based oxide electrocatalyst with highly uniform dispersion of iridium and ruthenium, high-activity ruthenium is introduced into the traditional iridium oxide, the oxygen evolution activity of the catalyst is improved, iridium is diluted, the use amount of iridium is reduced, and the corrosion resistance of the ruthenium catalyst is improved through the synergistic effect of iridium and ruthenium. The preparation method of the multi-element metal oxide developed by the invention is simple and feasible in industry, has higher operability and scalability, and is very suitable for mass production. The catalyst with low iridium loading capacity, high efficiency and high reliability prepared by the preparation method is beneficial to solving the technical problem of overhigh cost caused by high iridium element content of the iridium catalyst in the prior art.
It is also pointed out that the oxygen evolution catalyst with porous structure and high specific surface area prepared by the invention is beneficial to exposing more active sites and improving the electrocatalytic performance, and the added pore-forming agent can be decomposed or volatilized at a temperature far lower than the roasting temperature, thereby avoiding the problem of difficult template removal during pore-forming by the traditional template method.
When the catalyst is applied to a membrane electrode, water, isopropanol and a membrane solution are added into an anode catalyst, namely an iridium ruthenium based oxygen evolution catalyst, and a catalyst slurry is prepared by ultrasonic and then sprayed on the surface of a proton exchange membrane; adding water, isopropanol and membrane solution into the cathode catalyst, preparing catalyst slurry by ultrasonic wave, spraying the catalyst slurry on the other surface of the proton exchange membrane, drying and hot-pressing to obtain the PEM electrolytic water membrane electrode.
The preparation method of the PEM electrolytic water film electrode is an ultrasonic atomization spraying method, and Ir is used x Ru y O 2 The mass ratio of the anode catalyst, water, isopropanol and the membrane solution is 1: 10; the cathode catalyst is a commercially purchased 20% pt/C catalyst, the mass ratio of the cathode catalyst, water, isopropanol and membrane solution being 1: 4-7, drying the ultrasonic atomized spray on a vacuum adsorption platform at 80 ℃, and performing hot pressing on a hot press at the temperature of 120-140 ℃ for 5min.
The high-activity iridium ruthenium oxide oxygen evolution catalyst prepared by the invention is applied to PEM (proton exchange membrane) water electrolysis hydrogen production, the use amount of iridium noble metal in the membrane electrode can be reduced to below 0.3mg/cm < 2 > from 1.5-4mg/cm < 2 > in the prior industry, the performance is not reduced in long-term service life examination, the use amount of noble metal iridium and the manufacturing cost of the membrane electrode are obviously reduced through the improvement of the performance of the electrocatalyst, and a practical and feasible low-cost path is provided for PEM hydrogen production equipment.
FIG. 2 is a schematic flow diagram 200 illustrating a process for preparing an iridium ruthenium based oxygen evolution catalyst in another embodiment of the present invention. As shown in fig. 2, in an embodiment, the dissolving the iridium precursor and the ruthenium precursor in the solvent to obtain the mixed solution includes:
s201, respectively adding an iridium precursor and a ruthenium precursor into a solvent to obtain an iridium precursor solution and a ruthenium precursor solution.
In this step, a specific step is provided how to add the iridium precursor and the ruthenium precursor to the solvent to obtain an iridium precursor solution and a ruthenium precursor solution, respectively.
S202, dropwise adding the iridium precursor solution into the ruthenium precursor solution to obtain a mixed solution.
In this step, a specific step of adding the iridium precursor solution dropwise to the ruthenium precursor solution to obtain a mixed solution is provided.
In this example, a specific embodiment of how to obtain the mixed solution from the iridium precursor and the ruthenium precursor is provided. In addition, in this embodiment, the stirring device may be used to stir the mixture solution gradually during the dropping process, so as to obtain a uniform mixture solution.
FIG. 3 is a schematic flow diagram 300 illustrating a process for preparing an iridium ruthenium based oxygen evolution catalyst in another embodiment of the present invention. As shown in fig. 3, in an embodiment, the adding a pore-forming agent and sodium nitrate into the mixed solution, and performing calcination washing after heating to obtain the iridium ruthenium oxide crude product includes:
s301, adding a pore-forming agent and sodium nitrate into the mixed solution in sequence.
The specific steps of sequentially adding the pore-forming agent and the sodium nitrate into the mixed solution are provided in the step.
And S302, mixing and heating at a first preset temperature to dry the solvent to obtain dry salt.
In this embodiment, a specific step of heating the mixed solution containing the pore-forming agent and the sodium nitrate, and then drying the mixed solution to obtain the dry salt is provided. During the drying process, the dry salt can also be obtained by stirring and slowly evaporating the solvent.
S303, putting the dry salt into a sintering furnace to be roasted to obtain a molten salt-oxide mixture, and cooling the mixture to a second preset temperature in the furnace.
In this step, a specific step of roasting the dry salt is provided. And naturally cooling the furnace to the second preset temperature after the roasting is finished.
S304, washing the cooled molten salt-oxide mixture through deionized water to obtain an oxide.
In this step a specific step is provided for washing the molten salt-oxide mixture after cooling, the purpose of washing being to remove the salts and eventually the oxides.
S305, drying the washed oxide at a third preset temperature to obtain an iridium ruthenium oxide crude product.
In the present step, a specific step of drying the washed oxide is provided, and the third predetermined temperature is 60 to 100 ℃.
In the present example, a specific embodiment of obtaining the iridium ruthenium oxide crude product from the mixed solution is provided.
FIG. 4 is a schematic flow diagram 400 illustrating a process for preparing an iridium ruthenium based oxygen evolution catalyst in another embodiment of the present invention. As shown in fig. 4, in an embodiment, the pre-leaching the crude iridium ruthenium oxide product with an acid solution, and washing and drying the pre-leaching to obtain the iridium ruthenium based oxygen evolution catalyst comprises:
s401, pre-leaching impurities in the iridium ruthenium oxide crude product by using an acid solution to obtain a solid product.
In the present step, there is provided a specific step of subjecting the iridium ruthenium oxide crude product to a pre-leaching treatment with the acid solution.
S402, washing the solid product through the deionized water until the pH value is neutral.
In this step, a specific step is provided for washing the solid product again, the pH value being made acidic due to the pre-leaching of the acid solution, and being made neutral.
And S403, drying the washed solid product at a fourth preset temperature to obtain the iridium ruthenium based oxygen evolution catalyst.
In this step, a specific step of drying the solid product to obtain the iridium ruthenium based oxygen evolution catalyst is provided. The fourth predetermined temperature is 60 to 100 degrees celsius.
In the present embodiment, a specific embodiment is provided in which the iridium ruthenium oxide crude product is subjected to the above steps to finally obtain the iridium ruthenium based oxygen evolution catalyst. The invention carries out post acid leaching treatment on the prepared catalyst, can completely remove soluble impurities, improves the crystallinity and purity of the product, greatly reduces the agglomeration degree and granularity of catalyst particles, improves the particle dispersion degree, and greatly prolongs the settling time of catalyst slurry prepared by using the catalyst compared with commercial iridium oxide, thereby ensuring the uniformity and consistency of the slurry during ultrasonic spraying, being beneficial to preparing a membrane electrode with high consistency and further improving the catalytic performance.
In one embodiment, the iridium precursor solution is added dropwise to the ruthenium precursor solution at a dropping rate of 1 to 15mL/min, wherein the metal concentration in the iridium precursor solution and the ruthenium precursor solution is 0.05 to 0.5mol/L.
In one embodiment, the mass ratio of the sodium nitrate to the metal precursor in the mixed solution is 5 to 30:1.
in one embodiment, the roasting temperature is 350-550 ℃, the heating rate is 2-10 ℃/min, and the roasting time is 0.5-3 hours.
In one embodiment, the molar ratio of the pore-forming agent to the metal of the mixed solution is 10 to 200:1, the reaction time of the pore-forming agent and the metal precursor in the mixed solution is 0.5 to 3 hours.
In one embodiment, the temperature of the pre-leaching is 60 to 120 degrees celsius and the pre-leaching time is 0.5 to 6 hours.
In one embodiment, the acid solution has an acid concentration of 0.05 to 2mol/L.
Besides the iridium ruthenium-based oxygen evolution catalyst, other metal precursors can be added into the mixed solution, wherein the other metals are one or more of Pt, rh, au, mn, fe, ni, co, ti, zr, sn, mo, ta, W and Sr.
Basic principle and operation process:
example 1:
weighing iridium tetrachloride and ruthenium trichloride according to the molar ratio Ir (iridium) Ru (ruthenium) =3:1, and respectively stirring and dissolving the iridium tetrachloride and the ruthenium trichloride in isopropanol to obtain an iridium precursor solution and a ruthenium precursor solution, wherein the metal concentration is 0.2mol/L; dropwise adding the iridium precursor solution into the ruthenium precursor solution at the speed of 2mL/min, and continuously stirring for 2h to obtain the mixed solution of iridium and ruthenium precursors; adding ammonium bicarbonate with the total molar weight of iridium and ruthenium being 50 times into the mixed solution, stirring and reacting for 1 hour, adding sodium nitrate with the total mass of iridium tetrachloride and ruthenium trichloride being 20 times into the mixed solution, and stirring and reacting for 2 hours; heating the solution at 80 ℃ and stirring at 600r/min, and slowly evaporating the solvent to dryness to obtain iridium ruthenium dry salt; putting the dry salt into a high-temperature sintering furnace, heating to 500 ℃ at the speed of 5 ℃/min, roasting for 1h at 500 ℃, cooling to room temperature along with the furnace after the drying, washing with deionized water for multiple times, centrifuging to remove residual salt, and drying in an oven at 80 ℃ to obtain an iridium ruthenium oxide crude product; and (2) taking a certain amount of concentrated sulfuric acid, adding the concentrated sulfuric acid into water to prepare a 0.5mol/L sulfuric acid solution, adding the crude product into an acid solution, refluxing for 2 hours at 80 ℃ to completely remove impurities, then carrying out solid-liquid separation on the product, washing the product with deionized water for multiple times until the product is neutral, and drying at 80 ℃ to obtain the high-purity iridium ruthenium oxide oxygen evolution catalyst.
The preparation method of the membrane electrode by using the iridium ruthenium oxide oxygen evolution catalyst as an anode catalyst comprises the following steps:
weighing a certain amount of iridium ruthenium oxide catalyst prepared in example 1 as an anode catalyst, wherein the mass ratio of the iridium ruthenium oxide catalyst to the anode catalyst is 1: sequentially adding water, isopropanol and the membrane solution into the solution 2 to 5 parts by weight, and performing ultrasonic treatment and homogenization for 0.5 hour respectively to obtain uniformly dispersed anode catalyst slurry; weighing a certain amount of 20% commercial platinum carbon as a cathode catalyst, wherein the mass ratio of the platinum carbon to the cathode catalyst is 1:10, sequentially adding water, isopropanol and the membrane solution into the reactor from 4 to 7, and performing ultrasonic treatment and homogenization for 0.5h to obtain uniform cathode catalyst slurry; respectively spraying anode catalyst slurry and anode catalyst slurry onto two surfaces of a Nafion117 membrane by using an ultrasonic spraying machine, drying on a vacuum adsorption platform at 80 ℃ for 10min, taking out, putting into a hot press fixture, and carrying out hot pressing at 140 ℃ for 5min to obtain the membrane electrode of which the anode is loaded with iridium ruthenium oxide. The membrane electrode prepared in this example was tested for catalyst loading using a gravimetric method, which finally converted to an anode iridium loading of 0.288mg/cm2.
FIG. 5 is a SEM-EDS schematic view of iridium ruthenium oxide produced in an example of the present invention. SEM-EDX characterization of the iridium ruthenium oxide prepared in the above manner, as shown in fig. 5, it can be seen that the iridium atoms and the ruthenium atoms are highly uniformly dispersed. FIG. 6 is a N2 adsorption/desorption curve of oxygen evolution catalysts of example 1 and comparative example 3 of the present invention, and as shown in FIG. 6, it can be seen that the catalysts have a porous structure with coexisting micro/meso pores, a large amount of micro pores are distributed in a concentrated manner within 3nm, and the specific surface area thereof is as high as 176m 2 /g。
FIG. 7 is a linear sweep voltammogram of oxygen evolution catalysts of example 1 and comparative example 3 of the present invention. As shown in FIG. 7, the overpotential of the prepared iridium ruthenium oxide catalyst was only 230mV at 10mA/cm2, which is 78mV lower than that of the commercial catalyst. FIG. 8 is a linear sweep voltammogram before and after the stability test of the oxygen evolution catalyst of example 1 of the present invention. As shown in FIG. 8, it was revealed that the overpotential at 10mA/cm2 was 243mV, which was decreased by only 13mV, indicating that the catalyst stability was good.
FIG. 9 is a plot of current density versus voltage for example 1 of the invention and comparative example 3 tested in a proton exchange membrane electrolyzer. As shown in FIG. 9, it can be seen that the concentration is 2A/cm 2 Single-slot power supply at 80 deg.CThe pressure is 1.87V, and the electrolytic efficiency reaches 79 percent (HHV).
Example 2:
the preparation method and the electrochemical test method of the iridium ruthenium based oxygen evolution catalyst are the same as the previous method, and the difference is that: the molar ratio of iridium to ruthenium is Ir Ru =3:2. Linear scanning is carried out in 0.5mol/L sulfuric acid at normal temperature, 10mA/cm 2 The overpotential was 256mV.
Comparative example 1:
the preparation method and the electrochemical test method of the iridium ruthenium based oxygen evolution catalyst are the same as those of the embodiment 1, except that: no pore-forming agent is added when preparing the iridium ruthenium oxide oxygen evolution catalyst. Linear scanning is carried out in 0.5mol/L sulfuric acid at normal temperature, 10mA/cm 2 The overpotential was 272mV.
Comparative example 2:
the preparation method and the electrochemical test method of the iridium ruthenium based oxygen evolution catalyst are the same as the prior method, and the difference is that: the late acidification treatment is not carried out when the iridium ruthenium oxide oxygen evolution catalyst is prepared. Linear scanning is carried out in 0.5mol/L sulfuric acid at normal temperature, 10mA/cm 2 The overpotential was 275mV.
Comparative example 3:
the commercial iridium oxide catalyst purchased from the market is used as the anode oxygen evolution catalyst after being washed with acid, refluxed and dried according to the same method, and the electrochemical performance test of the rest catalysts, the preparation of the membrane electrode, the total noble metal loading capacity and the test of the water electrolyzer are the same as the previous method.
In addition, from the N2 adsorption/desorption curve of FIG. 6, it can be seen that the content of micropores of commercial iridium oxide is small and the specific surface area thereof is only 19m 2 (iv) g. As can be seen from the linear voltammogram of FIG. 4, the linear scan was performed in 0.5mol/L sulfuric acid at room temperature, 10mA/cm 2 The overpotential of commercial iridium oxide is 308mV, which is far higher than 230mV of the method, which indicates that the iridium ruthenium-based oxygen evolution catalyst prepared by the method has higher oxygen evolution activity. FIG. 7 shows commercial iridium oxide at 2A/cm 2 The voltage of the single cell at 80 ℃ is 1.96V, which is higher than 1.87V of example 1.
The results show that the iridium ruthenium-based oxygen evolution catalyst prepared by the method has far higher oxygen evolution activity than that of commercial iridium oxide, and the water electrolysis efficiency of the commercial iridium oxide is lower than that of the previous method even if more iridium is used.
The above embodiments are only exemplary embodiments of the present invention, and are not intended to limit the present invention, and the scope of the present invention is defined by the claims. Various modifications and equivalents may be made by those skilled in the art within the spirit and scope of the present invention, and such modifications and equivalents should also be considered as falling within the scope of the present invention.

Claims (8)

1. A method for preparing an iridium ruthenium based oxygen evolution catalyst is characterized by comprising the following steps:
dissolving an iridium precursor and a ruthenium precursor in a solvent to obtain a mixed solution;
adding a pore-forming agent and sodium nitrate into the mixed solution, heating, and roasting and washing to obtain an iridium ruthenium oxide crude product;
and (2) carrying out pre-leaching treatment on the iridium ruthenium oxide crude product by using an acid solution, washing and drying to obtain the iridium ruthenium based oxygen evolution catalyst, wherein the pre-leaching temperature is 60-120 ℃, the pre-leaching time is 0.5-6 hours, and the acid concentration of the acid solution is 0.05-2 mol/L.
2. The method of preparing an iridium ruthenium based oxygen evolution catalyst according to claim 1, wherein the dissolving an iridium precursor and a ruthenium precursor in a solvent to obtain a mixed solution comprises:
respectively adding an iridium precursor and a ruthenium precursor into a solvent to obtain an iridium precursor solution and a ruthenium precursor solution;
and dropwise adding the iridium precursor solution into the ruthenium precursor solution to obtain a mixed solution.
3. The preparation method of the iridium ruthenium based oxygen evolution catalyst according to claim 1 or 2, wherein the step of adding a pore former and sodium nitrate into the mixed solution, and performing calcination and washing after heating to obtain the iridium ruthenium oxide crude product comprises the following steps:
adding a pore-forming agent and sodium nitrate into the mixed solution in sequence;
mixing and heating at a first preset temperature to dry the solvent to obtain dry salt;
putting the dry salt into a sintering furnace for roasting to obtain a molten salt-oxide mixture, and cooling to a second preset temperature in the furnace;
washing the cooled molten salt-oxide mixture by deionized water to obtain an oxide;
and drying the washed oxide at a third preset temperature to obtain an iridium ruthenium oxide crude product.
4. The method for preparing an iridium ruthenium based oxygen evolution catalyst according to claim 3, wherein the pre-leaching of the iridium ruthenium oxide crude product with an acid solution, and washing and drying to obtain the iridium ruthenium based oxygen evolution catalyst comprises:
pre-leaching impurities in the iridium ruthenium oxide crude product by using an acid solution to obtain a solid product;
washing the solid product by the deionized water until the pH value is neutral;
and drying the washed solid product at a fourth preset temperature to obtain the iridium ruthenium-based oxygen evolution catalyst.
5. The method of preparing an iridium ruthenium based oxygen evolution catalyst according to claim 2, wherein the dropping rate of the iridium precursor solution to the ruthenium precursor solution dropwise is 1 to 15mL/min, wherein the metal concentration in the iridium precursor solution and the ruthenium precursor solution is 0.05 to 0.5mol/L.
6. The method of manufacturing an iridium ruthenium based oxygen evolution catalyst according to claim 1, wherein a mass ratio of the sodium nitrate to the metal precursor in the mixed solution is 5 to 30:1.
7. the method of preparing an iridium ruthenium-based oxygen evolution catalyst according to claim 3, wherein the calcination temperature is 350 to 550 ℃, the temperature rise rate is 2 to 10 ℃/min, and the calcination time is 0.5 to 3 hours.
8. The method of producing an iridium ruthenium based oxygen evolution catalyst according to claim 4, wherein the metal molar ratio of the pore-forming agent to the mixed solution is 10 to 200:1, the reaction time of the pore-forming agent and the metal precursor in the mixed solution is 0.5 to 3 hours.
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