CN115805317A - Ruthenium-iridium alloy material and preparation method and application thereof - Google Patents
Ruthenium-iridium alloy material and preparation method and application thereof Download PDFInfo
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- CN115805317A CN115805317A CN202211465645.3A CN202211465645A CN115805317A CN 115805317 A CN115805317 A CN 115805317A CN 202211465645 A CN202211465645 A CN 202211465645A CN 115805317 A CN115805317 A CN 115805317A
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- 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 invention discloses a ruthenium-iridium alloy material and a preparation method and application thereof, wherein the ruthenium-iridium alloy material is prepared by the following method: adding iridium chloride and ruthenium chloride serving as metal sources into a mixed solution of N-methylpyrrolidone and formic acid, and fully stirring; heating and synthesizing the ruthenium-iridium alloy consisting of the ultra-small nano particles by a solvothermal method. The method takes iridium chloride and ruthenium chloride as metal sources, takes N-methyl pyrrolidone as a solvent, and synthesizes the ruthenium-iridium alloy with a fingerprint shape by a solvothermal method under the reduction action of formic acid.
Description
Technical Field
The invention relates to the technical field of acidic electrochemical oxygen evolution, in particular to a ruthenium-iridium alloy material and a preparation method and application thereof.
Background
Fossil fuels such as petroleum coal have become a major energy source since the industrial revolution, and the excessive use of fossil fuels causes serious environmental problems such as greenhouse effect. Therefore, the realization of carbon emission reduction and the search of clean energy have received wide attention. Hydrogen energy is used as a zero-carbon green energy source and becomes an energy source with development prospect. Therefore, hydrogen energy technology has been intensively studied in recent decades.
The acidic electrochemical oxygen evolution technology is an important component of the technology for synthesizing hydrogen by electrocatalytic hydrolysis, and many technical problems still exist after decades of researches. Electrochemical oxygen evolution, as an anodic reaction for the synthesis of hydrogen by electrocatalytic hydrolysis, leads to its kinetic inertness since the reaction is a 4-electron transfer reaction. Therefore, the preparation of the acidic electrochemical oxygen evolution catalyst becomes one of the bottlenecks in the development of the technology for synthesizing hydrogen by electrocatalytic hydrolysis. Because of the high requirements for catalyst stability under acidic conditions, the currently preferred catalysts are mainly iridium-based catalysts. However, the intrinsic activity of the iridium-based catalyst is insufficient, and the requirement of industrial hydrogen production by water electrolysis is difficult to achieve.
Disclosure of Invention
Aiming at the defects of the prior art, the technical problem to be solved by the invention is how to prepare a novel catalyst material and improve the intrinsic activity and the electrochemical stability of the acidic electrochemical oxygen evolution catalyst.
In order to solve the technical problems, the first aspect of the invention provides a preparation method of a ruthenium-iridium alloy material, which comprises the following steps:
s1, adding iridium chloride and ruthenium chloride serving as metal sources into a mixed solution of N-methylpyrrolidone and formic acid, and fully stirring;
s2, heating and synthesizing the ruthenium-iridium alloy consisting of the ultra-small nano particles by a solvothermal method.
Further, in the step S1, the concentration of the iridium chloride after mixing is less than or equal to 1.5mg/mL.
Further, in the step S1, the concentration of the mixed ruthenium chloride is not more than 1.5mg/mL.
Further, in step S1, the volume ratio of N-methylpyrrolidone to formic acid is 2.
Further, in the step S2, the temperature rise temperature is 100 to 120 ℃.
The invention provides a ruthenium-iridium alloy material prepared by the preparation method.
The second aspect of the invention provides an application of the ruthenium-iridium alloy material, and the ruthenium-iridium alloy material is used as a catalyst in an acidic electrocatalytic oxygen evolution reaction.
Further, when the ruthenium-iridium alloy material is used as a catalyst, the ruthenium-iridium alloy material is dispersed in a solvent to obtain a catalyst solution, and the catalyst solution is coated on the working electrode.
Further, when the ruthenium-iridium alloy material is used as a catalyst, the working potential of the acidic electrocatalytic oxygen evolution reaction is 1.3-2.0V.
Further, when the ruthenium iridium alloy material is used as a catalyst, the current density is 10mA/cm in 0.5mol/L sulfuric acid aqueous solution 2 When the overvoltage is less than 250mV, the constant current works for 150 hours, and the potential drop rate is less than 5 percent.
Compared with the prior art, the invention has the following beneficial effects:
(1) The preparation method is simple and feasible, and the fingerprint ruthenium-iridium alloy consisting of ultra-small nano particles is synthesized in one step by taking iridium chloride and ruthenium chloride as metal sources and N-methylpyrrolidone as a solvent under the reduction action of formic acid through a solvothermal method.
(2) According to the invention, the ruthenium iridium alloy is formed by replacing iridium on the surface with ruthenium, and the structure of the metal iridium and the charge distribution on the surface of the metal iridium can be adjusted through synthesis, so that the ruthenium iridium alloy has a special appearance and an optimized electronic structure, and the intrinsic activity and stability of the ruthenium iridium alloy are improved.
(3) The ruthenium-iridium alloy has excellent catalytic activity and stability in the acidic electrocatalytic oxygen evolution reaction, and has good application prospect when being used as an anode catalyst for hydrogen production by water electrolysis of a proton exchange membrane.
Drawings
FIG. 1 is an X-ray diffraction pattern of a ruthenium-iridium alloy produced in example 1 of the present invention;
FIG. 2 is a TEM image of Ru-Ir alloy according to example 1 of the present invention;
FIG. 3 is a high-resolution TEM image of Ru-Ir alloy prepared in example 1 of the present invention;
FIG. 4 is a distribution diagram of elements of a ruthenium-iridium alloy according to example 1 of the present invention;
FIG. 5 is a linear scan graph of the materials of example 1, comparative example 1 and comparative example 2 of the present invention as catalysts in an acidic electrocatalytic oxygen evolution reaction;
FIG. 6 is a graph of stability tests of the materials of example 1 of the present invention and comparative example 1 as catalysts.
Detailed Description
In order to make the aforementioned objects, features and advantages of the present invention comprehensible, embodiments accompanied with figures are described in detail below.
It is to be understood that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. Further, for numerical ranges in this disclosure, it is understood that each intervening value, between the upper and lower limit of that range, is also specifically disclosed. Every smaller range between any stated value or intervening value in a stated range and any other stated or intervening value in a stated range is encompassed within the invention. The upper and lower limits of these smaller ranges may independently be included or excluded in the range.
It will be apparent to those skilled in the art that various modifications and variations can be made in the specific embodiments of the present disclosure without departing from the scope or spirit of the disclosure. Other embodiments will be apparent to those skilled in the art from consideration of the specification. The specification and examples are exemplary only.
The invention provides a ruthenium-iridium alloy material and a preparation method thereof, wherein iridium chloride and ruthenium chloride are used as metal sources, N-methylpyrrolidone is used as a solvent, and a fingerprint-shaped ruthenium-iridium alloy consisting of ultra-small nanoparticles is synthesized by a solvothermal method under the reduction action of formic acid, wherein the intrinsic activity and the stability of an iridium catalyst are improved by doping ruthenium. The preparation method is simple and feasible, and is synthesized in one step by a solvothermal method.
In a specific embodiment, the concentration of iridium chloride in the reaction system is less than or equal to 1.5mg/mL, the concentration of ruthenium chloride is less than or equal to 1.5mg/mL, and the volume ratio of N-methylpyrrolidone to formic acid is 2-4. The iridium chloride and the ruthenium chloride are fully mixed and heated to 100-120 ℃ for reaction, under the reduction action of formic acid, ruthenium replaces iridium on the surface to form ruthenium-iridium alloy, and the structure of the metal iridium and the charge distribution on the surface of the metal iridium are adjusted to improve the intrinsic activity and the stability of the metal iridium.
The ruthenium-iridium alloy material can be used as a catalyst in an acidic electrocatalytic oxygen evolution reaction, and as an implementation mode, the fingerprint-shaped ruthenium-iridium alloy material consisting of the ultra-small nanoparticles is dispersed in a solvent to obtain a catalyst solution, and the catalyst solution is coated on a working electrode. The working potential of the acidic electrocatalytic oxygen evolution reaction is 1.3-2.0V; the solvent used is not limited, and as an implementation mode, the solvent is composed of deionized water, ethanol and a binder.
The ruthenium-iridium alloy has high-efficiency acidic electrocatalytic oxygen evolution activity in an acidic electrocatalytic oxygen evolution reaction and has high stability. The current density in 0.5mol/L sulfuric acid aqueous solution is 10mA/cm 2 When the overvoltage is less than 250mV, the constant current works for 150 hours, and the potential drop rate is less than 5 percent.
The technical effects of the present invention will be described below with reference to specific examples.
Example 1
The preparation method of the ruthenium-iridium alloy comprises the following specific steps:
dissolving 5mg of iridium chloride and 5mg of ruthenium chloride in 5ml of a mixed solution of N-methylpyrrolidone and formic acid (volume ratio is 3; heating the solution to 100 ℃ and maintaining the temperature for 5 hours; washing and centrifuging for three times, putting the mixture into an oven, and drying the mixture for 12 hours at 70 ℃ to obtain ruthenium-iridium alloy powder.
The ruthenium-iridium alloy powder obtained in this example was analyzed by X-ray diffraction, and as a result, as shown in fig. 1, characteristic peaks of ruthenium and iridium were observed in fig. 1, which confirmed that the ruthenium-iridium alloy was synthesized by the above method.
The ruthenium-iridium alloy powder prepared by the embodiment is analyzed by a transmission electron microscope, and the test result is shown in fig. 2 and fig. 3, so that the material is observed to be ruthenium-iridium nanoparticles with the particle size less than 1nm, and the shape of the material is fingerprint-shaped.
The ruthenium-iridium alloy material prepared by the embodiment is used as an electrocatalyst for acidic electrocatalytic oxygen evolution, and the process is as follows:
(1) Preparation of catalyst ink
Weighing 4mg of the ruthenium iridium alloy powder prepared above and 4mg of carbon paste powder, adding to 735 mu L of deionized water and 235 mu L of ethanol, adding 30 mu L of 5% Nafion117 solution, and performing ultrasonic dispersion for half an hour to obtain the catalyst ink.
(2) Linear scan test
The electrocatalysis performance characterization of the catalyst is carried out by using an electrochemical workstation electrochemical three-electrode system of Shanghai Chenghua CHI760E type. 0.5mol/L sulfuric acid aqueous solution is used as electrolyte, a platinum mesh electrode is used as a counter electrode, and 250 mu L of catalytic ink is dripped on hydrophilic carbon paper to be used as a working electrode.
In the test, a linear scan test was performed in a potential range of 1.23 to 1.8V at a reversible hydrogen electrode, and as a result, as shown in FIG. 3, the ruthenium-iridium alloy catalyst of the present example was operated at a current density of 10mA/cm 2 When the overpotential is 237mV, the catalyst has very high catalytic activity.
(3) Stability test
The stability test was conducted using the test system as described in the above (2), and the results are shown in FIG. 4, in which the ruthenium-iridium alloy catalyst of the present example was used at a current density of 10mA/cm 2 The operation lasts for 150 hours, and the potential does not drop obviouslyThe catalyst is proved to have excellent stability.
Example 2
The preparation method of the ruthenium-iridium alloy comprises the following specific steps:
dissolving 1mg of iridium chloride and 5mg of ruthenium chloride in 5ml of a mixed solution of N-methylpyrrolidone and formic acid (volume ratio is 3; heating the solution to 110 ℃ and maintaining the temperature for 5 hours; washing and centrifuging for three times, putting the mixture into an oven, and drying the mixture for 12 hours at 70 ℃ to obtain ruthenium-iridium alloy powder.
The ruthenium-iridium alloy material prepared by the embodiment is used as an electrocatalyst for acidic electrocatalytic oxygen evolution, and the process is the same as that of the embodiment 1. The current density in 0.5mol/L sulfuric acid aqueous solution is 10mA/cm 2 The overpotential is 243mV; the potential did not drop significantly when the galvanostatic operation was carried out for 150 hours.
Example 3
The preparation method of the ruthenium-iridium alloy comprises the following specific steps:
dissolving 3.5mg of iridium chloride and 2mg of ruthenium chloride in 5ml of a mixed solution of N-methylpyrrolidone and formic acid (volume ratio is 3; heating the solution to 120 ℃ and maintaining the temperature for 5 hours; washing and centrifuging for three times, putting the mixture into an oven, and drying the mixture for 12 hours at 70 ℃ to obtain ruthenium-iridium alloy powder.
The ruthenium-iridium alloy material prepared by the embodiment is used as an electrocatalyst for acidic electrocatalytic oxygen evolution, and the process is the same as that of the embodiment 1. The current density in 0.5mol/L sulfuric acid aqueous solution is 10mA/cm 2 The overpotential is 246mV; the potential did not drop significantly when the galvanostatic operation was carried out for 150 hours.
Comparative example 1
In this comparative example, commercial iridium dioxide was used as an electrocatalyst for acidic electrocatalytic oxygen evolution, the procedure was the same as in example 1. As shown in FIGS. 3 and 4, the catalyst of comparative example 1 was used at a current density of 10mA/cm 2 The overpotential is significantly greater than the catalyst of example 1, indicating a lower activity; when the catalyst is operated for 4 hours under constant current, the catalyst is quickly deactivated, which shows that the stability of the catalyst is poor.
Comparative example 2
In this example, the preparation process of the material was as follows:
dissolving 5mg of iridium chloride in 5ml of a mixed solution of N-methylpyrrolidone and formic acid (volume ratio is 3; heating the solution to 100 ℃ and maintaining the temperature for 5 hours; washing and centrifuging for three times, putting into an oven, and drying for 12 hours at 70 ℃ to obtain metal powder.
The material prepared in the embodiment is used as an electrocatalyst for acidic electrocatalytic oxygen evolution, and the process is the same as the steps (1) and (2) in the embodiment 1. The test results are shown in FIG. 3, and the catalyst of comparative example 2 was used at a current density of 10mA/cm 2 The overpotential is greater than the catalyst of example 1, indicating lower activity.
Comparative example 3
In this example, the preparation process of the material was as follows:
dissolving 5mg of ruthenium chloride in 5ml of a mixed solution of N-methylpyrrolidone and formic acid (volume ratio is 3; heating the solution to 100 ℃ and maintaining the temperature for 5 hours; washed and centrifuged three times, finally put into an oven and dried for 12 hours at 70 ℃, and no product is obtained. Indicating that no metal nanoparticles were formed when only ruthenium chloride was added as the metal source.
Although the present disclosure has been described above, the scope of the present disclosure is not limited thereto. Those skilled in the art can make various changes and modifications without departing from the spirit and scope of the present disclosure, and such changes and modifications will fall within the scope of the present invention.
Claims (10)
1. A preparation method of a ruthenium-iridium alloy material is characterized by comprising the following steps:
s1, adding iridium chloride and ruthenium chloride serving as metal sources into a mixed solution of N-methylpyrrolidone and formic acid, and fully stirring;
s2, heating and synthesizing the ruthenium-iridium alloy consisting of the ultra-small nanoparticles by a solvothermal method.
2. The method for preparing a ruthenium-iridium alloy material according to claim 1, wherein the concentration of iridium chloride after mixing in step S1 is 1.5mg/mL or less.
3. The method for preparing a ruthenium iridium alloy material according to claim 1, wherein the concentration of ruthenium chloride after mixing is 1.5mg/mL or less in the step S1.
4. The method for preparing a ruthenium iridium alloy material according to claim 1, wherein in the step S1, the volume ratio of N-methylpyrrolidone to formic acid is 2 to 1.
5. The method for preparing a ruthenium iridium alloy material according to any one of claims 1 to 4 wherein the temperature rise in step S2 is from 100 to 120 ℃.
6. A ruthenium-iridium alloy material produced by the production method according to any one of claims 1 to 5.
7. The use of a ruthenium iridium alloy material as claimed in claim 6, wherein the ruthenium iridium alloy material is used as a catalyst in an acidic electrocatalytic oxygen evolution reaction.
8. The use according to claim 7, wherein the ruthenium iridium alloy material is dispersed in a solvent to obtain a catalyst solution, and the catalyst solution is coated on the working electrode.
9. Use according to claim 8, characterized in that the operating potential of the acidic electrocatalytic oxygen evolution reaction is between 1.3 and 2.0V.
10. Use according to claim 9, characterized in that the current density is 10mA/cm in a 0.5mol/L aqueous solution of sulfuric acid 2 When the overpotential is less than 250mV, the constant current works for 150 hours, and the potential drop rate is less than 5 percent.
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| CN117564289A (en) * | 2024-01-12 | 2024-02-20 | 中国科学技术大学 | Iridium ruthenium gold core-shell structure nano material and preparation method and application thereof |
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| CN117564289A (en) * | 2024-01-12 | 2024-02-20 | 中国科学技术大学 | Iridium ruthenium gold core-shell structure nano material and preparation method and application thereof |
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