KR20220079796A - Manufacturing method of ruthenium iridium nanoalloy using laser-irradiated acoustic suspension droplets - Google Patents

Abstract

The present invention discloses a method for preparing a ruthenium iridium nanoalloy using laser-irradiated acoustic suspension droplets. In the above method, after dissolving ruthenium salt, iridium salt and polyvinylpyrrolidone in ethylene glycol, acoustic suspension treatment is performed to obtain suspended droplets, and laser irradiation treatment is performed on the suspended droplets to prepare a ruthenium iridium nanoalloy including the steps of The present invention has opened a new path for the production of ruthenium iridium nanoalloys with simple operation, rapid, controllable trace amounts, and low energy consumption.

Description

Manufacturing method of ruthenium iridium nanoalloy using laser-irradiated acoustic suspension droplets

The present invention relates to a method for manufacturing a ruthenium iridium nanoalloy using laser-irradiated acoustic suspension droplets, and belongs to a novel manufacturing technology field of noble metal nanomaterials.

Since the information disclosed in the background section is only for increasing the understanding of the overall background of the present invention, it is acknowledged that the information constitutes prior art known to those of ordinary skill in the art or in any form. It should not be taken as implied.

Due to their intrinsic dimensional effects, surface effects and electronic states, metal nanoparticles are used in fields such as catalysis (CN 111185220 A), sensing (CN 111398396 A), optics (CN 111253936 A), medicine and biotechnology (CN 111420057 A). It has broad application prospects. Since various metal elements all have unique electronic arrangement states, alloying can obtain a different electronic structure from a single metal element, which can affect its performance in different applications. Numerous studies have shown that the major factors influencing nanoalloy performance are the dimensions of the alloy (J Am ChemSoc, 2014, 136(19):6978), elemental ratio (J Am ChemSoc, 2017, 139(13): 4643) and internal component distribution (Nat Chem, 2014, 6(4): 320). Therefore, it has significant scientific significance and engineering value to realize precise control of dimensions of nanoalloys, arbitrary combinations of components, and control of component distribution by developing a new manufacturing technology.

Ruthenium is a polyvalent rare metal element. Because of its stable properties, strong corrosion resistance, high hardness, and excellent electrical and catalytic properties, it is often used as a catalyst for cemented carbide, electrical contact alloy production and hydrogenation, oxidation, isomerization and reforming reactions (CN 111500914 A). Iridium is a rare precious metal material, considered as a metal element with the best corrosion resistance, and has excellent thermal stability, so it is mainly used in the production of crucibles for high-temperature reaction, scientific instruments, thermocouples, resistance wires, etc. Like other platinum group metal alloys, iridium alloys can strongly adsorb organic substances and can be used as catalyst materials (CN 111389395 A). Ruthenium and iridium have high mutual solubility, and the composition of the ruthenium-iridium alloy can be continuously adjusted within a relatively large range. By making ruthenium and iridium as an alloy, the advantages of both properties can be complemented. Currently, ruthenium-iridium alloy is used as a high-temperature thermocouple material, a catalyst, an antitumor material, and a light-emitting material.

Since ruthenium iridium nanoalloy has unique properties different from bulk alloy materials, realizing the controllable fabrication of ruthenium iridium nanoalloy is an effective means of extending its performance and application. According to the research of the present inventors, the nanoalloy manufacturing method that is currently widely adopted is to cause a reaction on a container or a substrate. This can easily cause heterogeneous nucleation, which can cause compositional segregation, make dimensional control impossible, and ultimately make the physicochemical properties of nanoalloys unstable. Therefore, it is urgent to develop a nanoalloy manufacturing method to realize precise dimensional control of materials, arbitrary combinations of components, and control of component distribution.

In order to solve the disadvantages of the prior art, it is an object of the present invention to provide a method for manufacturing a ruthenium iridium nanoalloy using a laser-irradiated acoustic suspension droplet. The present invention can overcome the problems of agglomeration and particle growth due to heterogeneous nucleation by implementing a containerless reaction to form ultrafine particles and mutually dissolving elements. A homogeneous alloy is formed by preventing component segregation that occurs during the reaction process. It instantaneously reaches the metal reduction temperature and forms a solid solution structure by simultaneously reducing different kinds of metal ions. By implementing micro-local vibration and micro-reaction, waste of raw materials and energy due to reaction in a conventional container is overcome. It also breaks through the limit of formation entropy to obtain a multi-component metastable alloy. Other alloy components and component distribution can be continuously adjusted.

The technical solution adopted in the present invention to implement the above object is as follows.

In one aspect, there is provided a method for producing a ruthenium iridium nanoalloy using laser irradiation acoustic suspension droplets, and after dissolving ruthenium salt, iridium salt and polyvinylpyrrolidone in ethylene glycol, acoustic suspension treatment is performed to obtain a suspension solution. A droplet is obtained, and a laser irradiation treatment is performed on the suspended droplet to prepare a ruthenium iridium nanoalloy.

The present invention uses acoustic suspension to allow the reaction process to be carried out in vesselless conditions. At the same time, it is possible to prevent the occurrence of heterogeneous nucleation by realizing rapid and simultaneous reduction of ruthenium and iridium metal ions by ethylene glycol through laser irradiation.

In another aspect, there is provided a ruthenium iridium nanoalloy prepared by the above method.

Advantageous effects of the present invention are as follows.

The present invention prepares ruthenium iridium nanoalloys through laser irradiation acoustic suspension droplets. The method realizes the reduction of ruthenium and iridium metal ions by ethylene glycol within 60 seconds, so that it is possible to produce a ruthenium iridium nanoalloy with uniform particle size, control of components and particle sizes, and excellent dispersibility. The particle size of the prepared ruthenium iridium nanoalloy can be continuously controlled within the range of 2 to 100 nm, the molar ratio of ruthenium and iridium can be adjusted within the range of 20:1 to 1:20, and the component distribution is uniform and controllable. The present invention can pave a new avenue for simple, rapid, low-energy, controllable fabrication of nanoalloys, and can promote the development of high-performance nanoalloy-related industries.

BRIEF DESCRIPTION OF THE DRAWINGS The accompanying drawings, which form a part of the present invention, are provided to aid the understanding of the present invention, and exemplary embodiments of the present invention and its description are for interpreting the present invention, and thus do not inappropriately limit the present invention.
1 is a transmission electron micrograph of the ruthenium iridium nanoalloy prepared in Example 1.
2 is a transmission electron microscope photograph of the ruthenium iridium nanoalloy prepared in Example 2.
3 is a transmission electron micrograph of the ruthenium iridium nanoalloy prepared in Example 3.
4 is a transmission electron microscope photograph of the ruthenium iridium nanoalloy prepared in Example 4.
5 is a transmission electron micrograph of the ruthenium iridium nanoalloy prepared in Example 5;

It is to be noted that all of the detailed descriptions below are exemplary and are intended to further explain the present invention. Unless otherwise specified, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art of this invention.

It should be noted that the terminology used herein is for the purpose of describing specific embodiments only, and is not intended to limit the exemplary embodiments according to the present invention. As used herein, the singular form is intended to include the plural form unless the context clearly dictates otherwise. It is also to be understood that the terms "comprising" and/or "inclusive of" as used herein indicate the presence of a feature, step, operation, element, component, and/or combination thereof.

In consideration of the disadvantages that heterogeneous nucleation is easy to generate, component segregation occurs, dimensional control is impossible, and manufacturing time is relatively long in the conventional method for manufacturing a ruthenium iridium nanoalloy, the present invention provides a ruthenium iridium nano using a laser irradiation acoustic suspension droplet. A method for manufacturing an alloy is proposed.

In a typical embodiment of the present invention, there is provided a method for producing a ruthenium iridium nanoalloy using laser irradiation acoustic suspension droplets, and after dissolving ruthenium salt, iridium salt and polyvinylpyrrolidone in ethylene glycol, acoustic suspension treatment is performed. to obtain suspended droplets, and laser irradiation treatment is performed on the suspended droplets to prepare a ruthenium iridium nanoalloy.

The present invention uses acoustic suspension to allow the reaction process to be carried out in vesselless conditions. At the same time, it is possible to prevent the occurrence of heterogeneous nucleation by realizing rapid and simultaneous reduction of ruthenium and iridium metal ions by ethylene glycol through laser irradiation.

The ruthenium salt according to the present invention refers to a compound in which a cation is a ruthenium ion, for example, ruthenium acetate.

The iridium salt according to the present invention refers to a compound in which a cation is an iridium ion, for example, iridium acetate.

In some embodiments of the above embodiment, the molar ratio of the ruthenium salt and the iridium salt is 0.05 to 20:1.

In some embodiments of the above embodiment, the concentration of the ruthenium salt in the reaction system is 5 to 100 mmol/L, and the concentration of the iridium salt is 5 to 100 mmol/L.

In some embodiments of the above embodiment, the concentration of polyvinylpyrrolidone in the reaction system is 0.1 to 50 g/L.

In some embodiments of the above embodiment, the volume of the suspension droplet is 1 to 200 μL.

In some embodiments of the above embodiment, when laser irradiation treatment, the output power of the laser is 10 to 80W.

In some embodiments of the above embodiment, the time of the laser irradiation treatment is 5 to 60 seconds.

In order to obtain a more pure ruthenium iridium nanoalloy, the pure method provided in some examples of the above embodiment is to centrifuge the suspended liquid after laser irradiation treatment.

In one or more embodiments, in the centrifugal purification process, the centrifugal rotation speed is 10000 to 13000 rpm, and the centrifugation time is 20 to 60 minutes.

In one or more embodiments, the number of centrifugal purification treatments is 3 to 6 times.

In one or more embodiments, the solvent employed for the centrifugal purification process is methanol, ethanol, propanol, isopropanol or water.

In one or more embodiments, drying is performed after centrifugal purification. Drying conditions are vacuum drying at 55 to 65 ℃ for 1 to 3 hours.

In another embodiment of the present invention, there is provided a ruthenium iridium nanoalloy prepared by the above method.

In one or more embodiments according to the above embodiments, the intensity is between 2 and 100 nm.

In order that those of ordinary skill in the art to which the present invention pertains can more clearly understand the technical solution of the present invention, the technical solution of the present invention will be described in detail below with specific examples.

Example 1:

25 μmol of ruthenium acetate, 25 μmol of iridium acetate, and 0.5 mg of polyvinylpyrrolidone were dissolved in 5 mL of ethylene glycol by ultrasonic waves to obtain a solution. Extract 35 µL of the solution with a syringe and transfer it to a uniaxial acoustic suspension autotuner to obtain suspension droplets. When the suspended droplet is irradiated with a laser for 10 seconds, ethylene glycol causes a reduction reaction with respect to ruthenium ions and iridium ions, and the laser output power is 50W. The suspension droplets after the reaction are collected in a centrifuge tube with a volume of 1.5 mL, methanol is added so that the total volume of the liquid is 1 mL, and centrifugal purification is performed in a centrifuge at a speed of 13000 rpm for 6 times to obtain a solid product. Each centrifugation time is 60 minutes. The solid product after centrifugal purification was transferred to a vacuum drying oven and dried at 60° C. for 2 hours to obtain a black ruthenium iridium nanoalloy.

As can be seen from the transmission electron micrograph of FIG. 1 , the particle size of the ruthenium iridium nanoalloy prepared in the above Example has a uniform distribution of about 2 nm, excellent particle dispersion, and no significant agglomeration phenomenon.

Example 2:

25 μmol of ruthenium acetate, 500 μmol of iridium acetate, and 0.1 g of polyvinylpyrrolidone were dissolved in 5 mL of ethylene glycol by ultrasonic waves to obtain a solution. Extract 35 µL of the solution with a syringe and transfer it to a uniaxial acoustic suspension autotuner to obtain suspension droplets. When the suspended droplet is irradiated with a laser for 10 seconds, ethylene glycol causes a reduction reaction with respect to ruthenium ions and iridium ions, and the laser output power is 40W. The suspension droplets after the reaction are collected in a centrifuge tube with a volume of 1.5 mL, ethanol is added so that the total volume of the liquid is 1 mL, and centrifugal purification is performed 5 times at a speed of 12000 rpm in a centrifuge to obtain a solid product. Each centrifugation time is 40 minutes. The solid product after centrifugal purification was transferred to a vacuum drying oven and dried at 60° C. for 2 hours to obtain a black ruthenium iridium nanoalloy.

According to the transmission electron micrograph of FIG. 2 , the particle size of the ruthenium iridium nanoalloy prepared in the above Example has a uniform distribution of about 3 to 5 nm, and has excellent particle dispersion and no agglomeration phenomenon.

Example 3:

500 μmol of ruthenium acetate, 25 μmol of iridium acetate and 0.2 g of polyvinylpyrrolidone were dissolved in 5 mL of ethylene glycol with ultrasonic waves to obtain a solution. Extract 20 µL of the solution with a syringe and transfer it to a uniaxial acoustic suspension auto-tuning device to obtain suspension droplets. When the suspended droplet is irradiated with a laser for 30 seconds, ethylene glycol causes a reduction reaction with respect to ruthenium ions and iridium ions, and the laser output power is 25W. The suspension droplets after the reaction are collected in a centrifuge tube with a volume of 1.5 mL, propanol is added so that the total volume of the liquid is 1 mL, and centrifugal purification is performed four times at a speed of 11000 rpm in a centrifuge to obtain a solid product. Each centrifugation time is 50 minutes. The solid product after centrifugal purification was transferred to a vacuum drying oven and dried at 60° C. for 2 hours to obtain a black ruthenium iridium nanoalloy.

According to the transmission electron micrograph of FIG. 3 , the particle size of the ruthenium iridium nanoalloy prepared in the above Example has a uniform distribution of about 8 to 10 nm, excellent particle dispersion, and no agglomeration phenomenon.

Example 4:

150 μmol of ruthenium acetate, 40 μmol of iridium acetate, and 0.125 g of polyvinylpyrrolidone were dissolved in 5 mL of ethylene glycol with ultrasonic waves to obtain a solution. Extract 25 µL of the solution with a syringe and transfer it to a uniaxial acoustic suspension auto-tuning device to obtain suspension droplets. When the suspended droplet is irradiated with a laser for 15 seconds, ethylene glycol causes a reduction reaction with respect to ruthenium ions and iridium ions, and the laser output power is 35W. The suspension droplets after the reaction are collected in a centrifuge tube with a volume of 1.5 mL, methanol is added so that the total volume of the liquid is 1 mL, and centrifugal purification is performed 5 times at a speed of 11500 rpm in a centrifuge to obtain a solid product. Each centrifugation time is 25 minutes. The solid product after centrifugal purification was transferred to a vacuum drying oven and dried at 60° C. for 2 hours to obtain a black ruthenium iridium nanoalloy.

According to the transmission electron micrograph of FIG. 4 , the particle size of the ruthenium iridium nanoalloy prepared in the above Example has a uniform distribution of about 12 to 15 nm, excellent particle dispersion, and no agglomeration phenomenon.

Example 5:

500 μmol of ruthenium acetate, 500 μmol of iridium acetate and 0.25 g of polyvinylpyrrolidone were dissolved in 5 mL of ethylene glycol by ultrasonic waves to obtain a solution. Extract 200 µL of the solution with a syringe and transfer it to a uniaxial acoustic suspension auto-tuning device to obtain suspension droplets. When the suspended droplet is irradiated with a laser for 60 seconds, ethylene glycol causes a reduction reaction with respect to ruthenium ions and iridium ions, and the laser output power is 20W. The suspension droplets after the reaction are collected in a centrifuge tube having a volume of 1.5 mL, water is added so that the total volume of the liquid is 1 mL, and centrifugal purification is performed three times at a speed of 10000 rpm in a centrifuge to obtain a solid product. Each centrifugation time is 20 minutes. The solid product after centrifugal purification was transferred to a vacuum drying oven and dried at 60° C. for 2 hours to obtain a black ruthenium iridium nanoalloy.

According to the transmission electron micrograph of FIG. 5 , the particle size of the ruthenium iridium nanoalloy prepared in the above Example is uniformly distributed to about 100 nm, and the particle dispersion is excellent and there is no agglomeration phenomenon.

The above contents are only relatively preferred embodiments of the present invention, and do not limit the present invention. Those skilled in the art to which the present invention pertains can variously change and change the present invention. All modifications, equivalent replacements, improvements, etc. according to the spirit and principle of the present invention should be included within the protection scope of the present invention.

Claims (10)

In the manufacturing method of a ruthenium iridium nanoalloy using laser irradiation acoustic suspension droplets,
After dissolving ruthenium salt, iridium salt and polyvinylpyrrolidone in ethylene glycol, acoustic suspension treatment is performed to obtain suspended droplets, and laser irradiation treatment is performed on the suspended droplets to prepare a ruthenium iridium nanoalloy. A method for producing a ruthenium iridium nanoalloy using laser-irradiated acoustic suspension droplets. According to claim 1,
A method for producing a ruthenium iridium nanoalloy using a laser irradiated acoustic suspension droplet, characterized in that the molar ratio of the ruthenium salt and the iridium salt is 0.05 to 20:1. According to claim 1,
The concentration of the ruthenium salt in the reaction system is 5 to 100 mmol/L, and the concentration of the iridium salt is 5 to 100 mmol/L. According to claim 1,
A method for producing a ruthenium iridium nanoalloy using a laser-irradiated acoustic suspension droplet, characterized in that the concentration of polyvinylpyrrolidone in the reaction system is 0.1 to 50 g/L. According to claim 1,
A method for producing a ruthenium iridium nanoalloy using a laser-irradiated acoustic suspension droplet, characterized in that the volume of the suspension droplet is 1 to 200 μL. According to claim 1,
A method of manufacturing a ruthenium iridium nanoalloy using laser irradiation acoustic suspension droplets, characterized in that during laser irradiation treatment, the output power of the laser is 10 to 80W. According to claim 1,
A method for producing a ruthenium iridium nanoalloy using laser irradiation acoustic suspension droplets, characterized in that the laser irradiation treatment time is 5 to 60 seconds. According to claim 1,
A method for producing a ruthenium iridium nanoalloy using laser-irradiated acoustic suspension droplets, characterized in that centrifugal stagnant treatment is performed on the suspended liquid after laser irradiation treatment. 9. The method of claim 8,
In the centrifugal purification treatment, the centrifugal rotation speed is 10000 to 13000 rpm, and the centrifugation time is 20 to 60 minutes;
The number of centrifugal purification treatments is 3 to 6 times;
The solvent employed for the centrifugal purification treatment is methanol, ethanol, propanol, isopropanol or water; or
A method for producing a ruthenium iridium nanoalloy using a laser-irradiated acoustic suspension droplet, characterized in that drying is performed after centrifugal refining. 10. A ruthenium iridium nanoalloy, characterized in that produced by the method according to any one of claims 1 to 9.

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