A Ru-Ir-M ternary alloy hollow nanocrystal and its synthesis method and application

Abstract

The present invention discloses a Ru-Ir-M ternary alloy hollow nanocrystal, its synthesis method and application, where M is Ag, Cu, Ni, or Co. The M metal and RuIr metal atoms form a hollow nanocrystal through a displacement reaction. The atomic vacancies formed in the displacement reaction migrate and diffuse to drive the immiscible Ru-Ir-M metals in the phase diagram to form a ternary alloy. Finally, the unalloyed M metal is etched away with HNO3 to obtain the Ru-Ir-M ternary alloy hollow nanocrystal, where the percentage of M in the total metal atoms is about 6% to 20%. The synthesis method has mild and non-toxic conditions, is simple, has a large yield, a low cost for the hollow structure, high dispersion of the particles, and the size of the nanocrystals can be effectively regulated by the size of the template metal particles, is suitable for large-scale production, and is used for the electrocatalytic oxygen evolution reaction, showing high activity and stability.

Description

Technical Field

[0001] The invention belongs to the field of material science, and particularly relates to a Ru-Ir-M ternary alloy hollow nanocrystal and a synthesis method and application thereof. Background Art

[0002] The combustion of fossil fuels has led to serious environmental problems such as ecological destruction, air pollution and global warming. Hydrogen is a clean renewable energy carrier that can power future transportation and other applications. Water electrolysis as a renewable resource to produce hydrogen is a promising field. To date, people have been working hard to develop electrocatalysts and membranes for water electrolysis technology. Water electrolysis in acidic media has better reaction kinetics than that in alkaline media, easy product separation and low operating pressure. Proton exchange membrane (PEM) water electrolysis is one of the most promising hydrogen production technologies. The oxygen evolution reaction (OER) occurring at the anode dominates the overall efficiency. However, most catalysts show unsatisfactory stability under strongly acidic and oxidizing conditions. Developing highly active and durable acidic OER electrocatalysts is a huge challenge for PEM water electrolysis.

[0003] The application of Ru and Ir-based oxide catalysts in acidic OER has attracted widespread attention. Studies have shown that Ru and Ir oxides are very easy to evolve into highly oxidized +6-valent or +8-valent soluble ions in strong acidic and oxidizing environments and dissolve in the electrolyte, making the material have poor catalytic stability. Stabilizing the valence state of RuIr and preventing it from becoming a high-valence state and losing in the acidic OER process has become a challenge for stabilizing catalysts. Some studies have formed alloys with Ru and other transition metals to affect their electronic structure and improve electrocatalytic activity and stability. After consulting the data, the solubility of Ru and Ir in Ag or Cu is extremely small. Some literature points out that phase separation occurs when the Ru content in the alloy exceeds 5% (at). For this situation where the ternary phase diagram is immiscible, there are very great challenges in synthesizing Ru-Ir-M ternary alloy hollow nanocrystals at the nanoscale. The extremely narrow alloy phase region poses a huge obstacle to the development of Ru and Ir-based ternary alloy catalysts. Summary of the invention

[0004] The invention provides a non-toxic, simple, ternary alloy, high uniformity, high concentration, low-cost synthesis method of Ru-Ir-M ternary alloy hollow nanocrystals and applies it to acidic electrocatalytic oxygen evolution reaction, overcoming the shortcomings of the prior art.

[0005] In order to achieve the above-mentioned purpose, the technical scheme adopted by the present invention is as follows: a method for synthesizing Ru-Ir-M ternary alloy hollow nanocrystals, wherein polyol and surfactant are stirred and fully preheated in an oil bath at 105-175°C, M nanoparticles are added, M is Ag, Cu, Ni or Co; the concentration is 0.71mM, and then Ru salt and Ir salt are added in sequence, the reaction solution is stirred evenly at 105-175°C, and is left at room temperature to fully react, during which the redox potential difference causes the M nanoparticles to undergo a substitution reaction with the Ru salt and the Ir salt, during which the atomic vacancy migration movement causes mutual diffusion between Ru, Ir and M atoms, so that the metal elements that are not mutually soluble in the phase diagram are alloyed; finally, HNO3 is used to etch and remove the M metal that has not been alloyed, so as to obtain Ru-Ir-M ternary alloy hollow nanocrystals, in which the percentage of M in the total metal atoms is 6%-20%.

[0006] The surfactant is polyvinyl pyrrolidone, polydiallyl dimethyl ammonium chloride, sodium citrate, hexadecyl trimethyl ammonium bromide, hexadecyl trimethyl ammonium chloride, sodium dodecyl sulfonate or sodium dodecyl sulfate.

[0007] The Ru salt is ruthenium chloride, ruthenium acetate, hexaammonium ruthenium trichloride or hexaammine ruthenium chloride, and the Ir salt is iridium chloride, iridium bromide or iridium acetylacetonate.

[0008] The polyol is ethylene glycol, diethylene glycol, triethylene glycol, 1,5-pentanediol or glycerol.

[0009] The hollow nanocrystals are synthesized by substitution between M nanoparticles and Ru salts and Ir salts due to the redox potential difference.

[0010] For silver nanoparticles, a one-step reduction method is used for synthesis, or a seed crystal reduction method is used to add a silver seed solution to a mixed solution of a reducing agent, a surfactant, and a silver salt;

[0011] For copper nanoparticles, a reducing agent, a surfactant and metal seed crystals are added into an organic solvent and synthesized by a seed crystal reduction method;

[0012] For nickel nanoparticles, nickel salt and a reducing agent are added to an aqueous solution of a surfactant for one-step reduction and centrifugation to obtain the nickel nanoparticles.

[0013] The Ru-Ir-M ternary alloy hollow nanocrystal obtained by the synthesis method of the invention has a ternary alloy hollow structure obtained by substitution through redox potential difference, and the thickness of the hollow nanocrystal ranges from 2.9 to 5.5 nm.

[0014] The Ru-Ir-M ternary alloy hollow nanocrystals of the present invention are used for electrocatalytic acidic oxygen evolution reaction.

[0015] Compared with the prior art, the invention has at least the following beneficial effects: the invention discloses a Ru-Ir-M, wherein M is Ag, Cu, Ni or Co; the synthesis of the ternary alloy hollow nanocrystals adopts non-toxic, green and environmentally friendly polyol as a solvent; the migration movement of atomic vacancies in the replacement reaction process causes the M atoms to form an alloy with the Ru and Ir atoms; the principle of the redox potential difference of the three atoms causes the M atoms to fully diffuse with the Ru and Ir atoms to form a ternary alloy; the metals that are immiscible in the phase diagram are effectively alloyed at the nanometer scale; the M metal in the Ru-Ir-M nanocrystals formed by the alloy modifies the electronic structures of Ru and Ir to change the adsorption energy, thereby improving the activity and stability in the electrocatalysis; at the same time, the nanoparticles with the hollow structure reduce the cost of the precious metal to a greater extent, and improve the catalytic utilization rate thereof; the size of the Ru-Ir-M ternary alloy hollow nanocrystals is regulated by the size of the M nanoparticles; the thickness of the ternary alloy hollow nanocrystals is regulated by changing the etching conditions; the preparation method of the invention is simple, the synthesis conditions are mild, the controllability is good, the particle dispersibility is high, the yield is high, the repeatability is high, and the invention is suitable for large-scale production.

[0016] Furthermore, the surfactant used in the synthesis of the Ru-Ir-M ternary alloy hollow nanocrystals of the present invention is easy to clean, and nanocrystals with clean surfaces can be obtained.

[0017] In the Ru-Ir-M ternary alloy hollow nanocrystals prepared by the invention, different M nanoparticles have different effects on the electrocatalytic performance of Ru and Ir.

[0018] The Ru-Ir-M ternary alloy hollow nanocrystals prepared by the present invention show excellent electrocatalytic performance, exhibit high activity and stability in acidic electrocatalytic oxygen evolution reaction, and can be applied to hydrogen production by electrolysis of water. BRIEF DESCRIPTION OF THE DRAWINGS

[0019] Figure 1 This is a transmission electron microscope image of the Ru-Ir-Ag (Ag content is 20%, thickness is about 4.5 nm) ternary alloy hollow nanocrystals prepared in Example 1.

[0020] Figure 2 This is a statistical thickness distribution picture of the Ru-Ir-Ag (Ag content is 20%, thickness is about 4.5nm) ternary alloy hollow nanocrystals prepared in Example 1.

[0021] Figure 3 This is a high-resolution transmission electron micrograph of the Ru-Ir-Ag (Ag content is 20%, thickness is about 4.5 nm) ternary alloy hollow nanocrystals prepared in Example 1.

[0022] Figure 4This is an X-ray diffraction spectrum (XRD) image of the Ru-Ir-Ag (Ag content is 20%, thickness is about 4.5 nm) ternary alloy hollow nanocrystals prepared in Example 1.

[0023] Figure 5 This is the EDS element distribution image of the Ru-Ir-Ag (Ag content is 20%, thickness is about 4.5nm) ternary alloy hollow nanocrystals prepared in Example 1.

[0024] Figure 6 This is a transmission electron microscope image of the Ru-Ir-Ag (Ag content is 20%, thickness is about 5.5 nm) ternary alloy hollow nanocrystals prepared in Example 2.

[0025] Figure 7 This is a statistical thickness distribution picture of the Ru-Ir-Ag (Ag content is 20%, thickness is about 5.5nm) ternary alloy hollow nanocrystals prepared in Example 2.

[0026] Figure 8 This is a transmission electron microscope image of the Ru-Ir-Ag (Ag content is 20%, thickness is about 2.9 nm) ternary alloy hollow nanocrystals prepared in Example 3.

[0027] Fig. 9 This is a statistical thickness distribution picture of the Ru-Ir-Ag (Ag content is 20%, thickness is about 2.9 nm) ternary alloy hollow nanocrystals prepared in Example 3.

[0028] Fig.10 This is a transmission electron microscope image of the Ru-Ir-Ag (Ag content is 6%, thickness is about 4.4nm) ternary alloy hollow nanocrystals prepared in Example 4.

[0029] Fig.11 This is a statistical thickness distribution picture of the Ru-Ir-Ag (Ag content is 6%, thickness is about 4.4nm) ternary alloy hollow nanocrystals prepared in Example 4.

[0030] Fig.12 This is a transmission electron micrograph of the Ru-Ir-Cu (Cu content is 20%) triple alloy hollow nanocrystals prepared in Example 5.

[0031] Fig.13 This is a transmission electron micrograph of the Ru-Ir-Ni (Ni content is 20%) triple alloy hollow nanocrystals prepared in Example 6.

[0032] Fig.14 These are polarization curves (LSV) of the oxygen evolution reaction of Ru-Ir-Ag (Ag content is 20%, thickness is 4.5 nm) ternary alloy hollow nanocrystals prepared in Example 1, commercial RuO2 and IrO2.

[0033] Fig.15 The oxygen evolution reaction of Ru-Ir-Ag (Ag content of 20%, thickness of 4.5nm) ternary alloy hollow nanocrystals prepared in Example 1, commercial RuO2 and IrO2 was 10mAcm -2 Constant current stability test picture.

[0034] Fig.16 The transmission electron microscope image of the silver nanoparticles prepared in Example 1 is shown.

[0035] Fig.17 This is a transmission electron microscopy image of the silver nanoparticles prepared in Example 2.

[0036] Fig.18 The transmission electron micrograph of the silver nanoparticles prepared in Example 3.

[0037] Fig.19 The transmission electron microscope image of the silver nanoparticles prepared in Example 4 is shown.

[0038] Fig. 20 This is a transmission electron microscopy image of the copper nanoparticles prepared in Example 5.

[0039] Fig.21 This is a transmission electron micrograph of the nickel nanoparticles prepared in Example 6. DETAILED DESCRIPTION

[0040] The present invention is further described in detail below in conjunction with specific examples, which are intended to explain the present invention rather than to limit it.

[0041] Preparation Example of Ru-Ir-M (M represents Ag, Cu, Ni or Co) Ternary Alloy Hollow Nanocrystals

[0042] Example 1

[0043] A method for synthesizing Ru-Ir-Ag (Ag content 20%, thickness about 4.5nm) ternary alloy hollow nanocrystals:

[0044] Polyvinyl pyrrolidone and ethylene glycol were placed in a 175°C oil bath and heated for 30 minutes, and then silver nanoparticles (concentration 0.71 mM) were added. Subsequently, Ru salt (concentration 0.28 mM) and Ir salt (concentration 0.14 mM) were added dropwise, reacted at 175°C for 2 hours, and left at room temperature for 48 hours. The material was centrifuged and etched with 20% HNO3 for 30 minutes to obtain Ru-Ir-Ag (Ag content 20%, thickness 4.5 nm) ternary alloy hollow nanocrystals.

[0045] The transmission electron microscope image of the Ru-Ir-Ag (Ag content of 20%, thickness of 4.5nm) ternary alloy hollow nanocrystals prepared in this example is as follows: Figure 1 As shown in the statistics. Figure 2 As shown in the figure, the hollow structure has a uniform morphology and a shell thickness of about 4.5±0.9nm. Figure 3 As shown, the X-ray diffraction spectrum (XRD) is as follows Figure 4 As shown, it shows that the arrangement of Ru-Ir-Ag atoms is characterized by long-range disorder and short-range order. The element analysis is as follows Figure 5 As shown, Ru, Ir and Ag are uniformly distributed.

[0046] Example 2

[0047] A method for synthesizing Ru-Ir-Ag (Ag content 20%, thickness about 5.5nm) ternary alloy hollow nanocrystals:

[0048] Polyvinyl pyrrolidone and ethylene glycol were placed in a 175°C oil bath and heated for 30 minutes, and then silver nanoparticles (concentration 0.71mM) were added. Subsequently, Ru salt (concentration 0.38mM) and Ir salt (concentration 0.19mM) were added dropwise, reacted at 175°C for 2 hours, and left at room temperature for 48h. The solution was centrifuged, washed and dispersed in water, 20% HNO3 was added, and left at room temperature for 48 hours to obtain Ru-Ir-Ag (Ag content 20%, thickness 5.5nm) ternary alloy hollow nanocrystals.

[0049] The transmission electron microscope image of the Ru-Ir-Ag (Ag content of 20%, thickness of 5.5nm) ternary alloy hollow nanocrystals prepared in this example is as follows: Figure 6 As shown in the statistics. Figure 7 As shown, the prepared hollow structure has a uniform morphology and a shell thickness of about 5.5±0.8nm.

[0050] Example 3

[0051] A method for synthesizing Ru-Ir-Ag (Ag content 20%, thickness about 2.9nm) ternary alloy hollow nanocrystals:

[0052] Polyvinyl pyrrolidone and ethylene glycol were placed in a 175°C oil bath and heated for 30 minutes, and then silver nanoparticles (concentration 0.71 mM) were added. Subsequently, Ru salt (concentration 0.19 mM) and Ir salt (concentration 0.09 mM) were added dropwise, reacted at 175°C for 2 hours, and left at room temperature for 48 hours. The material was centrifuged and etched with 30% HNO3 for 30 minutes to obtain Ru-Ir-Ag (Ag content 20%, thickness 2.9 nm) ternary alloy hollow nanocrystals.

[0053] The transmission electron microscope image of the Ru-Ir-Ag (Ag content of 20%, thickness of 2.9nm) ternary alloy hollow nanocrystals prepared in this example is as follows: Figure 8 As shown in the statistics. Fig. 9 As shown, the prepared hollow structure has a uniform morphology and a shell thickness of about 2.9±0.7nm.

[0054] Example 4

[0055] A method for synthesizing Ru-Ir-Ag (Ag content 6%, thickness about 4.4nm) ternary alloy hollow nanocrystals:

[0056] Polyvinyl pyrrolidone and ethylene glycol were placed in a 175°C oil bath and heated for 30 minutes, and then silver nanoparticles (concentration 0.71 mM) were added. Subsequently, Ru salt (concentration 0.28 mM) and Ir salt (concentration 0.14 mM) were added dropwise in sequence and reacted at 175°C for 2 hours. The material was centrifuged and etched with 60% HNO3 in a 80°C water bath for 48 hours to obtain Ru-Ir-Ag (Ag content 6%, thickness 4.4 nm) ternary alloy hollow nanocrystals.

[0057] The transmission electron microscope image of the Ru-Ir-Ag (Ag content of 6%, thickness of 4.4nm) ternary alloy hollow nanocrystals prepared in this example is as follows: Fig.10 As shown in the statistics. Fig.11 As shown, the prepared hollow structure has a uniform morphology and a shell thickness of about 4.4±0.9 nm.

[0058] Example 5

[0059] A method for synthesizing Ru-Ir-Cu (Cu content is 20%) ternary alloy hollow nanocrystals:

[0060] Polydiallyldimethylammonium chloride and triethylene glycol were placed in a 105°C oil bath and heated for 30 minutes, and then copper nanoparticles (concentration 0.71mM) were added. Subsequently, Ru salt (concentration 0.28mM) and Ir salt (concentration 0.14mM) were added dropwise, reacted at 105°C for 2h, and left at room temperature for 48 hours. The material was centrifuged and etched with 30% HNO3 solution for 30 minutes to obtain Ru-Ir-Cu (Cu content 20%) ternary alloy hollow nanocrystals.

[0061] The transmission electron microscope image of the Ru-Ir-Cu (Cu content is 20%) ternary alloy hollow nanocrystals prepared in this example is as follows: Fig.12 shown.

[0062] Example 6

[0063] A method for synthesizing Ru-Ir-Ni (Ni content is 20%) ternary alloy hollow nanocrystals:

[0064] Hexadecyltrimethylammonium bromide and 1,5-pentanediol were placed in a 140°C oil bath and heated for 30 minutes, and then nickel nanoparticles (concentration 0.71 mM) were added. Subsequently, Ru salt (concentration 0.24 mM) and Ir salt (concentration 0.14 mM) were added dropwise in sequence, and reacted at 140°C for 2 hours. The material was centrifuged and etched with a 30% HNO3 solution for 30 minutes to obtain Ru-Ir-Ni (Ni content 20%) ternary alloy hollow nanocrystals.

[0065] The transmission electron microscope image of the Ru-Ir-Ni (Ni content is 20%) ternary alloy hollow nanocrystals prepared in this example is as follows: Fig.13 shown.

[0066] 2. Application of Ru-Ir-M ternary alloy hollow nanocrystals in electrocatalytic oxygen evolution reaction

[0067] The Ru-Ir-Ag (Ag content of 20%, thickness of 4.5nm) ternary alloy hollow nanocrystals prepared in the above Example 1 were selected for testing; commercial RuO2 and IrO2 purchased on the market were used as controls, and the experimental process was as follows:

[0068] The prepared Ru-Ir-M ternary alloy hollow nanocrystals were dispersed in a solution prepared by water and isopropanol solution in a volume ratio of 2:1 to form a suspension with a RuIr concentration of 0.8 mg / mL. The contents of metal Ru, Ir and Ag in the suspension were measured by inductively coupled plasma mass spectrometry (ICP-MS). Ru+Ir ) The suspension was dropped onto the carbon cloth and dried naturally. Electrocatalytic oxygen evolution reaction experiments were carried out under a three-electrode system, where the electrolyte was a 0.1M oxygen-saturated perchloric acid solution and the scan rate was 10mV / s. The LSV results are shown in Fig.14 As shown, it shows that Ru-Ir-Ag ternary alloy hollow nanocrystals have a -2 The overpotential is much lower than that of commercial RuO2 and IrO2. To test the stability, -2 The results of the constant current analysis showed that the material did not show obvious overpotential changes for 200 hours. Fig.15 In contrast, commercial RuO2 and IrO2 were deactivated in 20 hours. The electrochemical test results show that Ru-Ir-Ag ternary alloy hollow nanocrystals have excellent activity and stability in acidic oxygen evolution reaction.

[0069] The M metal nanoparticles of the present invention can be prepared by the following examples.

[0070] Examples of preparing silver nanoparticles of different sizes using different seed concentrations:

[0071] Example 1, the synthesis of 23 nm silver nanoparticles with ascorbic acid as a reducing agent, comprising the following steps:

[0072] a. Preparation of silver seed solution

[0073] Polyvinyl pyrrolidone, sodium borohydride and silver nitrate were added into water, stirred vigorously at 30° C. for 30 minutes, and allowed to stand for 12 hours to age, thereby obtaining a silver seed solution.

[0074] b. Preparation of silver nanoparticles

[0075] Polyvinyl pyrrolidone, acetonitrile, ascorbic acid and silver nitrate were added into water and stirred evenly at 30° C., and a silver seed solution with a concentration of 0.59 mM was quickly added thereto, and the mixture was stirred at 30° C. for 1 hour to obtain silver nanoparticles.

[0076] The transmission electron microscope image of the silver nanoparticles prepared in this example is as follows: Fig.16 As shown, according to statistics, the size of the prepared silver balls is about 23nm and the morphology and structure are uniform.

[0077] Example 2

[0078] The synthesis of 360 nm silver nanoparticles with ascorbic acid as a reducing agent comprises the following steps:

[0079] a. Preparation of silver seed solution

[0080] This step is consistent with the method for preparing the silver seed solution in Example 1.

[0081] b. Preparation of silver nanoparticles

[0082] Polyvinyl pyrrolidone, acetonitrile, ascorbic acid and silver nitrate were added to water and stirred at 30°C, and a silver seed solution with a concentration of 0.55 mM was quickly added, and the solution was stirred at 30°C for 1 hour to obtain silver nanoparticles. The silver nanoparticles with larger particle size were obtained by reducing the seed concentration.

[0083] The transmission electron microscope image of the silver nanoparticles prepared in this example is as follows: Fig.17 As shown, according to statistics, the size of the prepared silver balls is about 360nm and the morphology and structure are uniform.

[0084] Implementation cases of preparing silver nanoparticles in one step using different reducing agents:

[0085] Example 3

[0086] Synthesis of silver nanoparticles with sodium citrate as a reducing agent:

[0087] Sodium citrate and silver nitrate were added into water and stirred at 100°C for 30 min to prepare silver nanoparticles.

[0088] The transmission electron microscope image of the silver nanoparticles prepared in this example is as follows: Fig.18 As shown, according to statistics, the size of the prepared silver nanoparticles is about 19 nm.

[0089] Example 4

[0090] Synthesis of silver nanoparticles with sodium borohydride as a reducing agent: Sodium borohydride and silver nitrate are added to water and stirred vigorously at room temperature for 1 hour to prepare silver nanoparticles; the transmission electron microscopy image of the silver nanoparticles prepared in this example is as follows Fig.19 As shown, according to statistics, the size of the prepared silver nanoparticles is about 14 nm, and the morphology and structure are uniform.

[0091] Examples of preparation of copper nanoparticles and nickel nanoparticles:

[0092] Example 5

[0093] Synthesis of a copper nanoparticle:

[0094] a. Preparation of platinum seeds

[0095] Sodium hypophosphite and chloroplatinic acid were added to water and reduced at 60°C for 1 hour to generate platinum nanocrystal seeds.

[0096] b. Preparation of copper nanoparticles

[0097] Copper nanoparticles were synthesized by crystal growth on platinum seeds. Potassium iodide, glycine, ethanolamine and platinum seeds were added to dimethylformamide and reacted at 140°C for 3 hours to produce copper nanoparticles.

[0098] The transmission electron microscope image of the copper nanoparticles prepared in this example is as follows: Fig. 20 As shown, the morphology and structure are uniform.

[0099] Example 6

[0100] Synthesis of a Nickel Nanoparticle:

[0101] Nickel nitrate and sodium borohydride were added to oleic acid and aqueous solution, stirred at room temperature for 1 hour, and collected by centrifugation to obtain nickel nanoparticles.

[0102] The transmission electron microscopy image of the nickel nanoparticles prepared in this example is as follows: Fig.21 As shown, the morphology and structure are uniform.

Claims

1. A method for synthesizing Ru-Ir-M ternary alloy hollow nanocrystals, characterized in that: The polyol and the surfactant are stirred and fully preheated in an oil bath at 105-175°C, and M nanoparticles are added, where M is Ag, Cu, Ni or Co; the concentration is 0.71 mM, and then Ru salt and Ir salt are added in sequence. The reaction solution is reacted at 105-175°C for two hours and left at room temperature for full reaction. During this process, the redox potential difference causes the M nanoparticles to undergo a replacement reaction with the Ru salt and the Ir salt. During the replacement reaction, the atomic vacancy migration movement causes the mutual diffusion between Ru, Ir and M atoms, so that the immiscible metal elements in the phase diagram are alloyed. Finally, HNO3 is used to etch and remove the unalloyed M metal to obtain Ru-Ir-M ternary alloy hollow nanocrystals, in which the percentage of M in the total metal atoms reaches 6%-20%, and the thickness of the Ru-Ir-M ternary alloy hollow nanocrystals ranges from 2.9 to 5.5 nm.

2. The method for synthesizing Ru-Ir-M ternary alloy hollow nanocrystals according to claim 1, characterized in that: The surfactant is polyvinyl pyrrolidone, polydiallyl dimethyl ammonium chloride, sodium citrate, hexadecyl trimethyl ammonium bromide, hexadecyl trimethyl ammonium chloride, sodium dodecyl sulfonate or sodium dodecyl sulfate.

3. The method for synthesizing Ru-Ir-M ternary alloy hollow nanocrystals according to claim 1, characterized in that: The Ru salt is ruthenium chloride, ruthenium acetate or hexaammonium ruthenium trichloride, and the Ir salt is iridium chloride, iridium bromide or iridium acetylacetonate.

4. The method for synthesizing Ru-Ir-M ternary alloy hollow nanocrystals according to claim 1, characterized in that: The polyol is ethylene glycol, diethylene glycol, triethylene glycol, 1,5-pentanediol or glycerol.

5. The method for synthesizing Ru-Ir-M ternary alloy hollow nanocrystals according to claim 1, characterized in that: For silver nanoparticles, a one-step reduction method is used for synthesis, or a silver seed solution is added to a mixed solution of a reducing agent, a surfactant, and a silver salt, and a seed reduction method is used for synthesis; For copper nanoparticles, a reducing agent, a surfactant and metal seeds are added to an organic solvent and synthesized by a seed reduction method; For nickel nanoparticles, nickel salt and a reducing agent are added to an aqueous solution of a surfactant for one-step reduction and centrifugation to obtain the nickel nanoparticles.

6. A Ru-Ir-M ternary alloy hollow nanocrystal, characterized in that: The compound is obtained by the synthesis method according to any one of claims 1 to 5.

7. The Ru-Ir-M ternary alloy hollow nanocrystals according to claim 6 are used for electrocatalytic acidic oxygen evolution reaction.

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