CN112725828B - IrRu-based multicomponent alloy metal precipitation catalyst and preparation method thereof - Google Patents

IrRu-based multicomponent alloy metal precipitation catalyst and preparation method thereof Download PDF

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CN112725828B
CN112725828B CN202011579958.2A CN202011579958A CN112725828B CN 112725828 B CN112725828 B CN 112725828B CN 202011579958 A CN202011579958 A CN 202011579958A CN 112725828 B CN112725828 B CN 112725828B
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irrux
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hydroxide
irru
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CN112725828A (en
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邹亮亮
刘培
刘得友
杨辉
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Ningbo Koko Innovation Energy Technology Co ltd
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    • Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis

Abstract

The application discloses an IrRu-based multicomponent alloy metal precipitation catalyst and a preparation method thereof, wherein the preparation method comprises the following steps: dissolving an iridium-containing compound, a ruthenium-containing compound and an X-containing metal compound in deionized water to form a precursor mixed solution; preparing an alkaline sacrificial carrier solution containing a strong base reagent; adding the precursor mixed solution into the alkaline sacrificial carrier solution, reacting to form IrRuX hydroxide, and loading the IrRuX hydroxide on the sacrificial carrier; and carrying out heat treatment on the IrRuX hydroxide in a reducing atmosphere to form the IrRuX alloy catalyst loaded on the sacrificial carrier. The IrRuX alloy catalyst has high stability and high catalytic activity.

Description

IrRu-based multicomponent alloy metal precipitation catalyst and preparation method thereof
Technical Field
The application relates to the technical field of solid electrolyte water electrolysis, in particular to an IrRu-based multi-component alloy metal precipitation catalyst with high activity and high stability and a preparation method thereof.
Background
With the increasingly prominent problems of resources, environment and energy resources on the earth, the development of renewable and environment-friendly energy resources is becoming a hot spot and a focus of international research and development. The hydrogen energy has the characteristics of high efficiency, environmental protection, rich resources and the like, and is widely applied. The development of hydrogen energy is not independent of hydrogen acquisition, storage, transportation and utilization, where hydrogen acquisition is a source of hydrogen energy economy and technology development. Hydrogen production by electrolysis of water is considered to be the most promising technology for the storage of renewable and sustainable energy sources. Compared with the alkaline water electrolysis technology, the acid Proton Exchange Membrane (PEM) electrolysis technology has the characteristics of larger current density, higher hydrogen purity, compact assembly, low ohmic loss, wide voltage load range and the like, the reaction rate in the acid electrolysis cell is higher than that in the alkaline electrolysis cell by more than three orders of magnitude, and the acid PEM electrolysis technology is very suitable for water electrolysis hydrogen production coupled with power generation of renewable energy sources (solar energy, wind energy and hydropower).
The anodic oxygen evolution reaction in the PEM is considered to be the main source of the overpotential of the electrolyzerAnd a large amount of experimental work and theoretical research show that the catalyst with better oxygen evolution catalytic activity under strong acid condition is mainly concentrated on IrO2、RuO2Etc. on the noble metal oxide. Wherein, RuO2The metal oxide is considered to have the highest oxygen evolution activity, but is easy to dissolve in an acidic system electrocatalytic environment, and has poor stability; IrO2The oxygen evolution activity is second to RuO2The stability is good, but the overpotential is 150-250 mV higher under the same current density, and the price is RuO25 to 7 times of the amount of the compound, thereby obtaining a binary composite metal oxide RuxIr1-xO2Both overpotential and catalyst cost can be reduced.
The patent CN111420658A adopts a hydrothermal method to prepare the IrRu alloy oxygen precipitation catalyst. In patent CN201110419158A, a silica molecular sieve is used as a template, and Ru and Ir noble metals are impregnated and reduced in a shell pore channel of the template to obtain the SPE water electrolysis anode catalyst. The study of Mazhari Abbasi et al finds that the rutile type IrO2-RuO2The formation of solid solution can simultaneously improve IrO2Electrocatalytic activity and RuO2Stability of the base. Kim et al found that IrO was prepared by electrochemical oxidationxAnd RuOxThe activity of the catalyst is higher than that of IrO prepared by a heat treatment method2And RuO2A catalyst.
However, the anode environment for hydrogen production by water electrolysis of solid electrolyte has strong oxidizability, and even metal simple substances can be converted into metal oxides in the anode environment. In addition, ruthenium in the alloy still dissolves out in acidity, so that the defects of black color caused by ruthenium dissolution, poor stability and the like still exist in the conventional various iridium ruthenium-based or alloy catalysts, and therefore, the development of a method capable of inhibiting ruthenium dissolution or improving ruthenium stability is urgently needed, so that the iridium ruthenium-based alloy catalyst with high activity and long durability is obtained.
Disclosure of Invention
In view of this, the present application provides an IrRu-based multicomponent alloy metal precipitation catalyst and a preparation method thereof, so as to solve the problem of poor stability of the existing IrRu-based catalyst.
The application provides a preparation method of an IrRu-based multicomponent alloy metal precipitation catalyst, which comprises the following steps: dissolving an iridium-containing compound, a ruthenium-containing compound and an X-containing metal compound in deionized water to form a precursor mixed solution; preparing an alkaline sacrificial carrier solution containing a strong base reagent; adding the precursor mixed solution into the alkaline sacrificial carrier solution, reacting to form IrRuX hydroxide, and loading the IrRuX hydroxide on the sacrificial carrier; and carrying out heat treatment on the IrRuX hydroxide in a reducing atmosphere to form an IrRuX alloy catalyst loaded on a sacrificial carrier, wherein the X metal can supplement oxygen atoms in time after Ru deoxidation.
Optionally, the X metal includes at least one of M metal or N metal, where M metal is W or Mo, and N metal is any one of La, Ce, Er, Sc, and Y.
Optionally, in the process of forming the precursor mixed solution, a surfactant or a complexing agent is further added.
Optionally, the surfactant or complexing agent comprises at least one of EDTA, CTAB, PVA, CTAC.
Optionally, the strong base reagent comprises at least one of potassium hydroxide and sodium hydroxide.
Optionally, the molar ratio of the strong alkali reagent to the sum of the Ir and the Ru is (5-20): 1.
Optionally, the sacrificial carrier includes at least one of nano silicon oxide, nano magnesium oxide, nano aluminum oxide and nano zinc oxide.
Optionally, the molar ratio of the sacrificial carrier to the sum of the Ir and the Ru is (5-20): 1.
Optionally, the temperature of the reaction system for forming the IrRuX hydroxide is 60-90 ℃, and the reaction time is 2-4 h.
Optionally, the method further includes: after the IrRuX hydroxide is formed, the IrRuX hydroxide-loaded sacrificial carrier is subjected to filtration, washing, and drying.
Optionally, the reducing atmosphere comprises at least one of hydrogen, carbon monoxide and ammonia.
Optionally, the heat treatment temperature is 300-800 ℃, and the heat treatment time is 2-24 h.
Optionally, the method further includes: after forming the IrRuX alloy catalyst loaded on the sacrificial carrier, filtering, washing and drying the sacrificial carrier loaded with the IrRuX alloy catalyst; alternatively, the sacrificial agent carrier is removed with an acid, and then washed and dried.
The application also provides an IrRu-based multi-component alloy metal precipitation catalyst, wherein the IrRu-based multi-component alloy is doped with X metal and has a general formula of IrxRuyXcWherein x is more than or equal to 0.5 and less than or equal to 0.75, y is more than or equal to 0.25 and less than or equal to 0.5, x + y is 1, and c is more than or equal to 0.05 and less than or equal to 0.2; the X metal can supplement oxygen atoms in time after the Ru deoxidization.
Optionally, the X metal includes at least one of M metal or N metal, where M metal is W or Mo, and N metal is any one of La, Ce, Er, Sc, and Y.
Optionally, the IrRu-based multicomponent alloy metal deposition catalyst has a particle size range of 3-7 nm.
According to the preparation method of the IrRu-based multi-component alloy catalyst, the IrRuX alloy catalyst is formed by introducing the doped metal X, and the metal X can supplement oxygen atoms in time after Ru deoxidation, so that Ru and H are reduced+The corrosion resistance of the catalyst is improved by contact, so that the stability of the catalyst is improved; in addition, agglomeration of IrRu alloy materials can be inhibited by introducing the doping metal X, so that particles become small, and the activity of the catalyst is improved. The method is simple to operate and easy to control, and can realize batch preparation.
In the preparation process, a surfactant or a complexing agent can be added to accelerate the dispersion of reactants and facilitate the reduction of the particle size of the catalyst.
Drawings
In order to more clearly illustrate the technical solutions in the embodiments of the present application, the drawings needed to be used in the description of the embodiments are briefly introduced below, and it is obvious that the drawings in the following description are only some embodiments of the present application, and it is obvious for those skilled in the art to obtain other drawings based on these drawings without creative efforts.
FIG. 1 is a schematic flow chart of a method for preparing an IrRu-based multicomponent alloy deposition catalyst according to an embodiment of the present disclosure;
FIG. 2 is an XRD pattern of the catalysts formed in examples 1 and 2 of the present application and the comparative example;
FIG. 3 is a linear scan curve of the catalysts formed in examples 1 and 2 of the present application and the comparative example;
FIG. 4 is a graph of current versus time for catalysts formed in examples 1 and 2 of the present application and comparative examples.
FIG. 5 is a TEM image of the catalyst formed in example 1 of the present application.
Detailed Description
The technical solutions in the embodiments of the present application are clearly and completely described below with reference to the accompanying drawings, and it is obvious that the described embodiments are only a part of the embodiments of the present application, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present application. The following embodiments and their technical features may be combined with each other without conflict.
Fig. 1 is a schematic flow chart of a method for preparing an IrRuX multicomponent alloy oxygen precipitation catalyst according to an embodiment of the present invention.
Step S101: dissolving an iridium-containing compound, a ruthenium-containing compound and an X-containing metal compound in deionized water to form a precursor mixed solution.
The iridium-containing compound, ruthenium-containing compound, and X-containing metal compound may be generally selected from metal salts. The X metal is taken as a doping metal and comprises at least one of M metal or N metal, wherein the M metal is W or Mo, and the N metal is any one of La, Ce, Er, Sc and Y. Wherein the mole fraction of Ir is x, and x is more than or equal to 0.5 and less than or equal to 0.75; the mole fraction of Ru is y, y is more than or equal to 0.25 and less than or equal to 0.5, and x + y is 1; the mole fraction of X is c, and c is more than or equal to 0.05 and less than or equal to 0.2.
Wherein, the X metal can supplement oxygen atoms in time after ruthenium is deoxidized, and reduce ruthenium and H+Contact and lifting the final shapeThe prepared catalyst has corrosion resistance, and further has the effect of improving the stability of the catalyst.
In the process of forming the precursor mixed solution, a surfactant or a complexing agent can be added and mixed uniformly. The compounds are uniformly dispersed in the solution by using a surfactant or a complexing agent. The surfactant or complexing agent comprises at least one of EDTA, CTAB, PVA and CTAC.
Step S102: an alkaline sacrificial carrier solution containing a strong base reagent is prepared.
The strong base reagent includes at least one of potassium hydroxide and sodium hydroxide such that the sacrificial support solution has a strong base. The molar ratio of the strong alkali reagent to the sum of the Ir and the Ru in the precursor mixed solution is (5-20) to 1. The PH value of the solution is more favorable for the sedimentation of Ir and Ru elements by adjusting the molar concentration of the strong alkali reagent. In some embodiments, the alkaline sacrificial carrier solution has a PH above 12.
The sacrificial carrier comprises at least one of nano silicon oxide, nano magnesium oxide, nano aluminum oxide and nano zinc oxide. The sacrificial carrier does not have other side reactions with other reactants, is not easy to decompose at high temperature, and is easy to remove subsequently.
After the sacrificial carrier is added into deionized water, the sacrificial carrier is uniformly dispersed in a mode of strong stirring or ultrasonic dispersion and the like; then adding strong alkali reagent KOH or NaOH to prepare alkaline sacrificial carrier solution.
Step S103: and adding the precursor mixed solution into the alkaline sacrificial carrier solution, reacting to form IrRuX hydroxide, and loading the IrRuX hydroxide on the sacrificial carrier.
In the process of adding the precursor mixed solution into the alkaline sacrificial carrier solution, the adding flow rate of the precursor mixed solution is strictly controlled, so that the liquid flows down without connecting a line, on one hand, the reaction of reactants in the precursor mixed solution and a strong base reagent is more sufficient, on the other hand, the intermediate product after the reaction can uniformly fall on the sacrificial carrier, and the subsequent final product particles are smaller and more uniform. Specifically, the precursor mixed solution may be added to the alkaline sacrificial carrier solution by dropwise addition.
The molar ratio of the sacrificial carrier to the sum of the two elements Ir and Ru is (5-20): 1.
And adding the precursor mixed solution into the alkaline sacrificial carrier solution, and reacting a reactant in the precursor mixed solution with a strong base reagent in the alkaline sacrificial carrier solution to form IrRuX hydroxide. The temperature of the reaction system is 60-90 ℃, and the reaction time is 2-4 h. After the reaction is completed, the IrRuX hydroxide-loaded sacrificial carrier is filtered, washed and dried.
Partial weakly reducing alcohols such as ethanol, isopropanol, etc. may also be added to the solution to enhance catalyst binding.
Step S104: and carrying out heat treatment on the IrRuX hydroxide in a reducing atmosphere to form the IrRuX alloy catalyst loaded on the sacrificial carrier.
The reducing atmosphere comprises at least one of hydrogen, carbon monoxide and ammonia. The heat treatment temperature is 300-800 ℃, and the heat treatment time is 2-24 h.
After the heat treatment is completed, N may be introduced2And taking out after cooling for 30 min. In other embodiments, cooling may be performed in other ways.
After the IrRuX hydroxide is formed, filtering, washing and drying the sacrificial carrier carrying the IrRuX alloy catalyst to remove impurities, thereby obtaining the IrRuX alloy catalyst with higher purity.
In other embodiments, after the IrRuX alloy catalyst supported on the sacrificial carrier is formed, the IrRuX alloy catalyst may be obtained by removing the sacrificial agent carrier with an acid, and then washing and drying the IrRuX alloy catalyst. Specifically, the IrRuX alloy catalyst is obtained by dissolving a sacrificial carrier carrying the IrRuX alloy catalyst in an acidic solution, for example, a 1mol/L sulfuric acid solution, removing the sacrificial carrier by acid leaching, and then washing and drying the sacrificial carrier. The pH value range of the acidic solution is 1-1.5.
The IrRu-based multi-component alloy catalyst prepared by the method has high oxygen evolution activity and high stability, and can be applied to electrocatalysis in an acidic environment. The method is simple to operate and easy to control, and can realize batch preparation.
In the process of oxygen precipitation of the IrRu alloy oxide catalyst adopted in the prior art in an acid environment, oxygen atoms are required to be provided, so that oxygen vacancies occur in the catalyst body, and H is generated+Contact with ruthenium metal results in dissolution of the ruthenium. In the invention, the doped metal X introduced into the IrRu-based multi-component alloy catalyst can supplement oxygen atoms in time after Ru deoxidization, so that Ru and H are reduced+The corrosion resistance of the catalyst is improved by contact, and the effect of improving the stability of the catalyst is further achieved. In addition, the doped metal X is introduced to inhibit the agglomeration of IrRu alloy materials, so that particles are reduced, and the activity of the catalyst is improved.
The following are some specific examples of forming IrRu-based multi-element alloy catalysts of the present invention.
Example 1
1) Preparing a metal precursor mixed solution: according to the molar ratio of Ir to Ru being 6 to 4, chloroiridic acid and ruthenium chloride are taken, erbium chloride hexahydrate accounting for 10 percent of the total molar weight of iridium and ruthenium is taken to be dissolved in deionized water, and the mixture is stirred until the mixture is completely dissolved; and adding a surfactant EDTA (ethylene diamine tetraacetic acid) with the total molar weight of iridium and ruthenium being 1% into the solution dissolved with the metal ions, stirring and uniformly mixing to prepare a precursor mixed solution.
2) Preparing an alkaline sacrificial carrier solution: taking strong base reagent KOH with the molar ratio of 5:1 to the total molar weight of iridium and ruthenium, taking sacrificial agent carrier nano magnesium oxide with the molar weight of KOH, dispersing the strong base reagent KOH and the sacrificial agent carrier nano magnesium oxide in deionized water, and strongly stirring to uniformly disperse the nano magnesium oxide and the deionized water.
3) Precipitation reaction: dropwise adding the metal precursor mixed solution into an alkaline sacrificial carrier solution mixed by a strong base reagent and a sacrificial carrier, controlling the reaction temperature at 90 ℃, reacting for 2 hours, filtering, washing and drying.
4) Heat treatment of the catalyst: carrying out heat treatment on the dried product for 6h under the conditions of reducing atmosphere and 400 ℃, and then introducing N2Cooling after 30min and taking out.
5) And (3) subsequent treatment: the sample after heat treatment is dissolved in 1mol/L sulfuric acid solution, the pH value is adjusted to 1.5,removing the sacrificial agent carrier by acid leaching, washing with deionized water and drying to obtain the required catalyst Ir0.6Ru0.4Er0.1。
Example 2
1) Preparing a metal precursor mixed solution: according to the mol ratio of Ir to Ru being 6 to 4, taking chloroiridic acid and ruthenium chloride, respectively taking erbium chloride hexahydrate with the mol amount of 5 percent of the total mol amount of iridium and ruthenium and tungsten chloride with the mol amount of 5 percent of the total mol amount of iridium and ruthenium, dissolving the mixture in deionized water, and stirring the mixture until the mixture is completely dissolved; and adding a surfactant EDTA (ethylene diamine tetraacetic acid) with the total molar weight of iridium and ruthenium being 1% into the solution dissolved with the metal ions, and uniformly stirring and mixing to obtain a precursor mixed solution.
2) Preparing a sacrificial carrier solution: taking strong base reagent KOH with the molar ratio of 5:1 to the total molar weight of iridium and ruthenium, taking sacrificial agent carrier nano magnesium oxide with the molar weight of KOH, dispersing the strong base reagent KOH and the sacrificial agent carrier nano magnesium oxide in deionized water, and strongly stirring to uniformly disperse the nano magnesium oxide and the deionized water.
3) Precipitation reaction: dropwise adding the metal precursor mixed solution into the strong base reagent and sacrificial agent carrier mixed solution, controlling the reaction temperature at 90 ℃, reacting for 2 hours, filtering, washing and drying;
4) heat treatment of the catalyst: and (3) carrying out heat treatment on the dried product for 6h under the conditions of reducing atmosphere and 400 ℃, introducing N for 230 min, and cooling and taking out.
5) And (3) subsequent treatment: dissolving the heat-treated sample in 1mol/L sulfuric acid solution, adjusting the pH to 1.5, taking out the sacrificial agent template by acid leaching, washing with deionized water and drying to obtain the required catalyst Ir0.6Ru0.4Er0.05W0.05。
Example 3
1) Preparing a metal precursor mixed solution: according to the molar ratio of Ir to Ru being 7 to 3, chloroiridic acid and ruthenium chloride are taken, erbium chloride hexahydrate accounting for 10 percent of the total molar weight of iridium and ruthenium is dissolved in deionized water, and the mixture is stirred until the mixture is completely dissolved; and adding a surfactant EDTA (ethylene diamine tetraacetic acid) with the total molar weight of iridium and ruthenium being 1% into the solution dissolved with the metal ions, stirring and uniformly mixing to prepare a precursor mixed solution.
2) Preparing a sacrificial carrier solution: taking a strong base reagent KOH with the molar ratio of 5:1 to the total molar weight of iridium and ruthenium, then taking a sacrificial agent carrier nano magnesium oxide with the molar weight of KOH, dispersing the two in deionized water, and strongly stirring to uniformly disperse the two;
3) precipitation reaction: dropwise adding the metal precursor solution into the mixed solution of the strong base reagent and the sacrificial agent carrier, controlling the reaction temperature at 90 ℃, reacting for 3 hours, filtering, washing and drying;
4) heat treatment of the catalyst: and (3) carrying out heat treatment on the dried product at 400 ℃ in a reducing atmosphere for 8h, introducing N for 230 min, and cooling and taking out.
5) And (3) subsequent treatment: dissolving the heat-treated sample in 1M sulfuric acid solution, adjusting the pH value to 1.5, removing the sacrificial agent template by acid leaching, washing with deionized water and drying to obtain the required catalyst Ir0.7Ru0.3Er0.1。
Example 4
1) Preparing a metal precursor mixed solution: according to the mol ratio of Ir to Ru, taking chloroiridic acid and ruthenium chloride in a ratio of 7 to 3, respectively taking erbium chloride hexahydrate accounting for 5 percent of the total molar weight of iridium and ruthenium and tungsten chloride accounting for 5 percent of the total molar weight of iridium and ruthenium, dissolving the mixture in deionized water, and stirring the mixture until the mixture is completely dissolved; and adding a surfactant EDTA (ethylene diamine tetraacetic acid) with the total molar weight of iridium and ruthenium being 1% into the solution dissolved with the metal ions, and uniformly stirring and mixing to obtain a precursor mixed solution.
2) Preparing a sacrificial carrier solution: taking a strong base reagent KOH with the molar ratio of 5:1 to the total molar weight of iridium and ruthenium, then taking a sacrificial agent carrier nano magnesium oxide with the molar weight of KOH, dispersing the two in deionized water, and strongly stirring to uniformly disperse the two;
3) precipitation reaction: dropwise adding the metal precursor solution into the mixed solution of the strong base reagent and the sacrificial agent carrier, controlling the reaction temperature at 90 ℃, reacting for 3 hours, filtering, washing and drying;
4) heat treatment of the catalyst: carrying out heat treatment on the dried product for 8h under the conditions of reducing atmosphere and 400 ℃, and then introducing N2Cooling after 30min and taking out.
5) And (3) subsequent treatment: dissolving the heat-treated sample in 1mol/L sulfuric acid solution, adjusting the pH to 1.5, taking out the sacrificial agent template by acid leaching, washing with deionized water and drying to obtain the required catalystOxidant Ir0.7Ru0.3Er0.05W0.05。
In order to better reflect the influence of the addition of the doped metal X on the performance of the multi-element alloy catalyst, the embodiment of the invention also provides a comparative example for forming the IrRu alloy catalyst.
Comparative example:
1) preparing a metal precursor mixed solution: taking chloroiridic acid and ruthenium chloride according to the molar ratio of Ir to Ru being 6: 4; adding a surfactant EDTA (ethylene diamine tetraacetic acid) with the total molar weight of iridium and ruthenium being 1% into the solution dissolved with the metal ions, and uniformly stirring and mixing to obtain a precursor mixed solution;
2) preparing a sacrificial carrier solution: taking a strong base reagent KOH with the molar ratio of 5:1 to the total molar weight of iridium and ruthenium, then taking a sacrificial agent carrier nano magnesium oxide with the molar weight of KOH, dispersing the two in deionized water, and strongly stirring to uniformly disperse the two;
3) precipitation reaction: dropwise adding the metal precursor solution into the mixed solution of the strong base reagent and the sacrificial agent carrier, controlling the reaction temperature at 90 ℃, reacting for 3 hours, filtering, washing and drying;
4) heat treatment of the catalyst: carrying out heat treatment on the dried product for 8h under the conditions of reducing atmosphere and 400 ℃, and then introducing N2Cooling after 30min and taking out.
5) And (3) subsequent treatment: and (3) dissolving the heat-treated sample in a 1mol/L sulfuric acid solution, adjusting the pH to 1.5, taking out the sacrificial agent template by acid leaching, washing with deionized water and drying to obtain the required catalyst.
Preparation of the catalyst Ir formed in the above comparative example0.6Ru0.4。
The invention also inspects the performance of the prepared IrRu-based multi-component alloy catalyst, mainly comprises XRD test, electrochemical test (linear scanning and i-t curve) and transmission electron microscope atlas, and comprises the following specific steps:
(1) XRD test: the IrRu-based multi-component alloy catalysts prepared in examples 1 and 2 and the comparative example were subjected to X-ray diffraction, and the corresponding XRD patterns were analyzed, as shown in fig. 2.
And (3) analyzing a test result: the alloy catalysts prepared in the examples 1 and 2 and the comparative example are formed by the alloy, but the comparative example not only forms the alloy, but also has the peak of the Ru simple substance, and after the doping element X is added in the examples 1 and 2, the peak of the Ru simple substance is continuously reduced until the peak disappears, so that the doping of the X metal is beneficial to the formation of the alloy.
And Ir obtained in example 2 was calculated by Scherrer's formula0.6Ru0.4Er0.05W0.05Ir with an average particle size of 3nm to 4nm as obtained in example 10.6Ru0.4Er0.1Average particle diameter of 6nm to 7nm, and Ir as obtained in the comparative example0.6Ru0.4The average particle diameter is 8nm-9 nm. It can be seen that the particle size of the catalyst is also reduced after the doping element is added, which is beneficial to improving the oxygen precipitation activity of the catalyst. Wherein, the particle size refers to the diameter of the catalyst nanoparticle.
(2) Electrochemical testing: each 10mg of IrRu-based catalyst prepared in example 1, example 2 and comparative example was dissolved in 2.8mL of pure water, and 0.2mL of 5 wt% Nafion solution was added to prepare a polymer solution (ink) having a total volume of 3mL, followed by sonication for 30 min. Coating the polymer solution on a platinum-carbon working electrode, taking an Ag/AgCl electrode as a reference electrode and a platinum sheet as a counter electrode to form a classical three-electrode system, and performing electrochemical reaction on the platinum-carbon working electrode in 0.1M HClO4In the solution, after nitrogen gas was introduced for 30min, the catalysts prepared in examples 1 and 2 and the control example were subjected to a linear scanning curve (see fig. 3) and a current-time (i-t) curve (see fig. 4). In FIG. 3, RHE is used to indicate that the reference electrode potential is a quasi-standard zero potential.
And (3) analyzing a test result: as shown in fig. 3, it can be seen from the linear scanning curves of the catalysts prepared in example 1, example 2 and comparative example that the voltage is lower for the catalysts of example 1 and example 2 compared to the comparative example at the same current density, indicating that the oxygen evolution activity is improved, especially at low current density, indicating that the addition of the metal element improves the activity of the catalyst. As shown in FIG. 4, Ir can be seen from the i-t curves of the catalysts prepared in example 1, example 2 and comparative example0.6Ru0.4Er0.1And Ir0.6Ru0.4Er0.05W0.05The oxygen precipitation performance in the acid electrolyte is all larger than Ir0.6Ru0.4The performance of the catalyst.
(3) Fig. 5 is a TEM (transmission electron microscope) image of the catalyst formed in example 1, and it can be seen from fig. 5 that the particle size distribution of the catalyst is uniform and the particle size is in accordance with the results in fig. 2.
The embodiment of the invention also provides an IrRu-based multi-component alloy metal precipitation catalyst, wherein the IrRu-based multi-component alloy is doped with X metal and has a general formula of IrxRuyXcWherein x is more than or equal to 0.5 and less than or equal to 0.75, y is more than or equal to 0.25 and less than or equal to 0.5, x + y is 1, and c is more than or equal to 0.05 and less than or equal to 0.2. The X metal can supplement oxygen atoms in time after ruthenium deoxidation, and reduce ruthenium and H+The contact improves the corrosion resistance of the finally formed catalyst, thereby playing a role in improving the stability of the catalyst.
The X metal comprises at least one of M metal or N metal, wherein the M metal is W or Mo, and the N metal is any one of La, Ce, Er, Sc and Y.
In some embodiments, the IrRu-based multicomponent alloy comprises: ir0.6Ru0.4Er0.1、Ir0.6Ru0.4Er0.05W0.05、Ir0.7Ru0.3Er0.1、Ir0.7Ru0.3Er0.05W0.05And the like.
The IrRu-based multicomponent alloy metal precipitated catalyst has a particle size range of 3-7 nm and high uniformity.
The X metal doped in the IrRu-based multi-element alloy catalyst can reduce the particle size of the catalyst and improve the oxygen precipitation activity of the catalyst and the stability of the catalyst in an acid environment.
The above-mentioned embodiments are only examples of the present application, and not intended to limit the scope of the present application, and all equivalent structures or equivalent flow transformations made by the contents of the specification and the drawings, such as the combination of technical features between the embodiments and the direct or indirect application to other related technical fields, are also included in the scope of the present application.

Claims (14)

1. A preparation method of an IrRu-based multicomponent alloy metal precipitation catalyst is characterized by comprising the following steps:
dissolving an iridium-containing compound, a ruthenium-containing compound and an X-containing metal compound in deionized water to form a precursor mixed solution;
preparing an alkaline sacrificial carrier solution containing a strong base reagent;
adding the precursor mixed solution into the alkaline sacrificial carrier solution, reacting to form IrRuX hydroxide, and loading the IrRuX hydroxide on the sacrificial carrier;
and carrying out heat treatment on the IrRuX hydroxide in a reducing atmosphere to form an IrRuX alloy catalyst loaded on a sacrificial carrier, wherein the X metal can supplement oxygen atoms in time after Ru deoxidation, and the X metal comprises at least one of M metal or N metal, wherein the M metal is W or Mo, and the N metal is any one of La, Ce, Er, Sc and Y.
2. The method according to claim 1, wherein the step of forming the precursor mixed solution further comprises adding a surfactant or a complexing agent.
3. The method of claim 2, wherein the surfactant or complexing agent comprises at least one of EDTA, CTAB, PVA, and CTAC.
4. The method of claim 1 wherein the alkali agent comprises at least one of potassium hydroxide and sodium hydroxide.
5. The preparation method according to claim 4, wherein the molar ratio of the strong alkali reagent to the sum of the two elements Ir and Ru is (5-20): 1.
6. The method according to claim 1, wherein the sacrificial support comprises at least one of nano silica, nano magnesia, nano alumina and nano zinc oxide.
7. The preparation method according to claim 6, wherein the molar ratio of the sacrificial support to the sum of the two elements Ir and Ru is (5-20): 1.
8. The preparation method according to claim 1, wherein the temperature of the reaction system for forming the IrRuX hydroxide is 60-90 ℃, and the reaction time is 2-4 h.
9. The method of claim 1, further comprising: after the IrRuX hydroxide is formed, the IrRuX hydroxide-loaded sacrificial carrier is subjected to filtration, washing, and drying.
10. The method of claim 1, wherein the reducing atmosphere comprises at least one of hydrogen, carbon monoxide, and ammonia.
11. The method according to claim 1, wherein the heat treatment temperature is 300 ℃ to 800 ℃ and the heat treatment time is 2h to 24 h.
12. The method of claim 1, further comprising: after forming the IrRuX alloy catalyst loaded on the sacrificial carrier, filtering, washing and drying the sacrificial carrier loaded with the IrRuX alloy catalyst; alternatively, the sacrificial carrier is removed with an acid, and then washed and dried.
13. The IrRu-based multi-component alloy metal precipitation catalyst is characterized in that the IrRu-based multi-component alloy is doped with X metal and has a general formula of IrxRuyXcWherein x is more than or equal to 0.5 and less than or equal to 0.75, y is more than or equal to 0.25 and less than or equal to 0.5, x + y is 1, and c is more than or equal to 0.05 and less than or equal to 0.2; the X metal can supplement oxygen atoms in time after Ru deoxidization, and the X metal comprises at least one of M metal or N metal, wherein the M metal is W metalOr Mo and N metal is any one of La, Ce, Er, Sc and Y.
14. The IrRu-based multicomponent alloy metal deposition catalyst of claim 13, wherein the IrRu-based multicomponent alloy metal deposition catalyst has a particle size ranging from 3 to 7 nm.
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