Preparation method of ultrafine amorphous platinum-ruthenium nanomaterial and application thereof

Abstract

This invention discloses a method for preparing ultrafine amorphous platinum-ruthenium nanomaterials and their applications, comprising the following steps: (1) Platinum acetylacetonate, hexadecyltrimethylammonium chloride and oleylamine are thoroughly mixed at room temperature, and molybdenum hexacarbonyl is added and reacted at 160-200℃ for 1-4h; (2) Under heat preservation conditions, oleylamine solution of dodecacarbonyltriruthenium is added to the material obtained in step (1), and the reaction is continued for 1-4h, and then naturally cooled to room temperature; (3) The material obtained in step (2) is thoroughly washed with a mixture of ethanol and n-hexane, and then centrifuged and redispersed in n-hexane to obtain a crystalline platinum-ruthenium nanowire dispersion; (4) The platinum-ruthenium nanowire dispersion obtained in step (3) is added to an activated carbon dispersion and ultrasonically treated at 15-25℃ for 1-3h, then the precipitate is collected by centrifugation, and vacuum drying and calcination in air are performed sequentially to obtain the ultrafine amorphous platinum-ruthenium nanomaterials. The ultrafine amorphous platinum-ruthenium nanomaterials prepared in this invention exhibit superior catalytic performance and excellent CO tolerance in the electrocatalytic reaction of hydroxide oxidation.

Description

Technical Field

[0001] This invention belongs to the field of catalyst material preparation technology, specifically relating to a method for preparing ultrafine amorphous platinum-ruthenium nanomaterials and their applications. Background Technology

[0002] Hydrogen-oxygen fuel cells have many advantages such as high energy conversion efficiency, environmental friendliness, and high energy density. They are a new type of clean energy with good development prospects and have attracted great attention from researchers (I. Staffell, D. Scamman, et al. Energy Environ. Sci. 2019, 12, 463.).

[0003] With the rapid development of anion exchange membranes in recent years (G. Das, JHChoi, et al. Polymers 2022, 14, 1197.), alkaline hydrogen-oxygen fuel cells have begun to attract widespread research. In alkaline media, some non-precious metal catalysts have achieved catalytic activity comparable to platinum catalysts (M. Liu, X. Xiao, et al. J. Colloid Interface Sci. 2022, 607, 791.). However, the anodic hydrogenation kinetics of platinum catalysts in alkaline media are 2-3 orders of magnitude lower than those in acidic media (J. Zheng, W. Sheng, et al. Sci. Adv. 2016, 2, e1501602.). Furthermore, industrially produced H2 contains trace amounts of CO, which can poison the active sites of the catalyst (X. Wang, Y. Li, et al. Proc. Natl. Acad. Sci. USA 2021, 118, e2107332118.), thus significantly reducing the catalytic performance of hydrogen oxidation. These factors greatly limit the development and application of alkaline hydrogen-oxygen fuel cells. Therefore, it is necessary to develop and design highly active electrocatalysts with high CO tolerance to improve the conversion efficiency of the hydrogen oxidation reaction, thereby promoting the large-scale application of alkaline hydrogen oxidation fuel cells.

[0004] Studies have shown that in alkaline media, an excessively strong hydrogen binding energy (HBE) on a single-component platinum catalyst is unfavorable for the further oxidation and desorption of adsorbed hydrogen (*H) on the catalyst surface, i.e., the Volmer step: *H + OH-. - / *OH→H2O+e -(M.Li, L.Li, et al. J. Phys. Chem. Lett. 2022, 13, 10550.). From the bifunctional mechanism (J.Li, S. Ghoshal, et al. Angew. Chem. Int. Ed. 2017, 56, 15594.), it is known that the slow kinetics of platinum hydroxide oxidation under alkaline conditions are due to two factors: firstly, the high concentration of hydroxide ions in the electrolyte competes with *H for adsorption, reducing the limited active sites on the catalyst surface; secondly, platinum has weak adsorption of hydroxyl groups (*OH), making it difficult for them to oxidize and desorb from adsorbed hydrogen at adjacent sites. Based on this, Markovic et al. (D. Strmcnik, M. Uchimura, et al. Nat. Chem. 2013, 5, 300.) reported on Pt... 0.1 Ru 0.9 Both Ni(OH)₂ / Pt(111) dual-site catalysts, which regulate *H and *OH respectively, exhibit higher catalytic activity than single-component platinum catalysts. Therefore, introducing a second oxygen-loving element (such as Ru, Ni, etc.) into a platinum catalyst is one of the effective means to improve the kinetics of hydroxide oxidation.

[0005] Furthermore, compared to crystalline materials, amorphous nanomaterials exhibit unique advantages in the field of electrocatalysis due to their abundant active sites, highly flexible atomic coordination environment, permeability of internal active sites to light elements, and high structural flexibility (S. Anantharaj, S. Noda, Small 2020, 16, e1905779.). For example, 1-nm thick amorphous PtSe... x The atom utilization rate reached as high as 26%, demonstrating hydrogen evolution activity far superior to that of single noble metal catalysts (Y.He, L.Liu, et al. Nat. Catal. 2022, 5, 212.). Jin Shangming et al. (W.Wang, T.He, et al. Nano Lett. 2021, 21, 3458.) also designed PdCu nanowires with a diameter of approximately 2.4 nm and applied them to the alkaline ethanol oxidation electrocatalytic reaction, achieving a mass activity as high as 15.25 A / mg, confirming that amorphization is an effective strategy for activating noble metal-based nanomaterials and promoting the catalytic process. However, due to the strong metallic bonds between noble metal atoms, the synthesis and structural control of amorphous noble metal nanomaterials have always faced significant technical challenges. Therefore, developing convenient and efficient amorphization synthesis strategies is crucial for improving the catalytic activity of alkaline hydrogen oxidation. Summary of the Invention

[0006] The purpose of this invention is to overcome the defects of the prior art and provide a method for preparing ultrafine amorphous platinum-ruthenium nanomaterials.

[0007] Another object of the present invention is to provide the application of the ultrafine amorphous platinum-ruthenium nanomaterials prepared by the above preparation method.

[0008] The technical solution of the present invention is as follows:

[0009] A method for preparing ultrafine amorphous platinum-ruthenium nanomaterials includes the following steps:

[0010] (1) After thoroughly mixing acetylacetonate platinum, hexadecyltrimethylammonium chloride and oleylamine at room temperature, add hexacarbonyl molybdenum and react at 160-200℃ for 1-4 hours;

[0011] (2) Under heat preservation conditions, add oleylamine solution of dodecyltriruthenium carbonyl to the material obtained in step (1), continue the heat preservation reaction for 1-4 hours, and then cool naturally to room temperature;

[0012] (3) Wash the material obtained in step (2) thoroughly with a mixture of ethanol and n-hexane, then centrifuge and redisperse it in n-hexane to obtain a crystalline platinum-ruthenium nanowire dispersion.

[0013] (4) Add the platinum-ruthenium nanowire dispersion obtained in step (3) to the activated carbon dispersion, sonicate at 15-25℃ for 1-3 hours, then centrifuge to collect the precipitate, and then vacuum dry and calcine in air to obtain the ultrafine amorphous platinum-ruthenium nanomaterial.

[0014] In a preferred embodiment of the present invention, in step (1), the ratio of acetylacetonate platinum, hexadecyltrimethylammonium chloride, hexacarbonylmolybdenum and oleylamine is 15-25mg:50-70mg:25-35mg:4-6mL.

[0015] More preferably, in the oleylamine solution of dodecyltriruthenium dodecylcarbonyl in step (2), the ratio of dodecyltriruthenium dodecylcarbonyl to oleylamine is 2-22 mg: 1-3 mL.

[0016] More preferably, the mass ratio of the platinum acetylacetonate to the ruthenium dodecylcarbonyl is 15-25:2-22.

[0017] In a further preferred embodiment, in step (4), the volume ratio of the platinum-ruthenium nanowire dispersion to the activated carbon dispersion is 0.3-0.7:1-3, and the concentration of activated carbon in the activated carbon dispersion is 1-3 mg / mL.

[0018] In a preferred embodiment of the present invention, the vacuum drying temperature is 40-60°C and the time is 8-15 hours.

[0019] In a preferred embodiment of the present invention, the calcination temperature is 180-220°C and the time is 1-3 hours.

[0020] The application of the ultrafine amorphous platinum-ruthenium nanomaterials prepared by the above method in the preparation of alkaline hydroxide reaction catalysts.

[0021] An alkaline hydroxide reaction catalyst, the raw material of which includes ultrafine amorphous platinum-ruthenium nanomaterials prepared by the above preparation method.

[0022] The beneficial effects of this invention are:

[0023] 1. This invention synthesizes ultrafine amorphous platinum-ruthenium nanomaterials via a one-pot liquid-phase chemical reduction method. Furthermore, by controlling the amount of ruthenium precursor salt added, ultrafine amorphous platinum-ruthenium nanomaterials with controllable ruthenium content and uniform morphology can be prepared. Finally, by utilizing an in-situ oxidation-induced amorphization strategy, crystalline platinum-ruthenium nanowires are successfully transformed into amorphous ultrafine platinum-ruthenium nanomaterials for use in alkaline hydrogenation electrocatalytic reactions.

[0024] 2. The preparation method of the present invention has simple and efficient experimental operation, is green and pollution-free, and has a high yield.

[0025] 3. The ultrafine amorphous platinum-ruthenium nanomaterials prepared by this invention have superior catalytic performance and excellent CO tolerance for the electrocatalytic reaction of hydroxide oxidation. Attached Figure Description

[0026] Figure 1 Transmission electron microscopy (TEM) images of ultrafine crystalline platinum-ruthenium nanomaterials with different ruthenium contents prepared in Examples 1 to 3 and Comparative Example 1 of the present invention: (a) Example 1; (b) Example 2; (c) Example 3; (d) Comparative Example 1.

[0027] Figure 2 The images show XRD comparisons of carbon-supported ultrafine crystalline platinum-ruthenium nanomaterials (c-Pt-Ru NWs / C) and carbon-supported ultrafine amorphous platinum-ruthenium nanomaterials (a-Pt-Ru NWs / C) with different ruthenium contents prepared in Examples 1 to 3 and Comparative Example 1 of this invention. (a) Carbon-supported ultrafine crystalline platinum-ruthenium nanomaterials (c-Pt-Ru NWs / C) and carbon-supported ultrafine amorphous platinum-ruthenium nanomaterials (a-Pt-Ru NWs / C) with different ruthenium contents; (b) Uncalcined carbon-supported platinum nanomaterials (Pt NWs / C) and calcined platinum nanomaterials (calcined-PtNWs / C).

[0028] Figure 3 The ultrafine crystalline platinum-ruthenium nanomaterial (c-Pt) prepared in Example 1 of this invention 53 Ru 47 NWs / C, carbon-supported, uncalcined) and ultrafine amorphous platinum-ruthenium nanomaterials (a-Pt) 53 Ru 47High-resolution transmission electron microscopy (HRTEM) images of NWs / C (carbon-loaded, calcined), (a, b) c-Pt 53 Ru 47 NWs / C;(c,d)a-Pt 53 Ru 47 NWs / C.

[0029] Figure 4 The ultrafine crystalline platinum-ruthenium nanomaterial (c-Pt) prepared in Example 1 of this invention 53 Ru 47 NWs / C, carbon-supported, uncalcined), ultrafine amorphous platinum-ruthenium nanomaterials (a-Pt) 53 Ru 47 Comparison of alkaline hydroxide activity between NWs / C (carbon-supported, calcined) and commercial platinum-ruthenium catalysts (PtRu / C) and commercial platinum-carbon catalysts (Pt / C): (a) Hydroxylation polarization curves of the catalysts; (b) Tafel curves of the catalysts; (c) Comparison of mass activity and specific activity of the catalysts.

[0030] Figure 5 The ultrafine crystalline platinum-ruthenium nanomaterial (c-Pt) prepared in Example 1 of this invention 53 Ru 47 NWs / C, carbon-supported, uncalcined), ultrafine amorphous platinum-ruthenium nanomaterials (a-Pt) 53 Ru 47 Comparison of CO tolerance between NWs / C (carbon-supported, calcined) and commercial platinum-ruthenium catalysts (PtRu / C) and commercial platinum-carbon catalysts (Pt / C). Detailed Implementation

[0031] The technical solution of the present invention will be further explained and described below with reference to specific embodiments and accompanying drawings.

[0032] Example 1

[0033] (1) In a 25 mL reaction flask, add 20 mg of platinum acetylacetonate, 60 mg of cetyltrimethylammonium chloride and 5 mL of oleylamine in sequence. Stir at room temperature for 20 min and sonicate for 20 min. Add the reducing agent molybdenum hexacarbonyl. Place in an oil bath and react at 180 °C for 3 h.

[0034] (2) Add an oleylamine solution containing 22 mg of dodecacarbonyltriruthenium to the material obtained in step (1), maintain the temperature at 180°C and continue the reaction for 3 hours. After the reaction is completed, allow it to cool naturally to room temperature.

[0035] (3) The material obtained in step (2) was thoroughly centrifuged and washed several times with a mixture of n-hexane and ethanol (volume ratio 1:1), and then redispersed in n-hexane to obtain a concentration of 2 mg / mL. Pt+Ru Crystalline platinum-ruthenium nanowire dispersion;

[0036] (4) Use a pipette to transfer 0.5 mL of the crystalline platinum-ruthenium nanowire dispersion obtained in step (3), add it to a glass bottle containing 2 mL of activated carbon dispersion (concentration of 2 mg / mL), sonicate at a water temperature of 15-25℃ for 2 h, collect by centrifugation, place it in a vacuum drying oven at 50℃ for 12 h, and finally transfer it to a muffle furnace and calcine it at a rate of 5℃ / min to 200℃ for 2 h in an air atmosphere to obtain ultrafine amorphous platinum-ruthenium nanomaterials.

[0037] The morphology, composition, and crystal structure of the products were systematically studied using modern analytical techniques such as TEM, ICP-MS, and XRD. Figures 1 to 3 As shown in Table 1, TEM characterization revealed that the product was a one-dimensional ultrafine nanowire structure. ICP-MS characterization revealed the Pt and Ru content in the product, with an atomic ratio of 53:47 (as shown in Table 1). XRD characterization revealed the crystal phase structure of the carbon-supported platinum-ruthenium nanomaterials before and after calcination in air. The crystalline platinum-ruthenium nanomaterials before calcination exhibited characteristic diffraction peaks of the Pt and Ru face-centered cubic phases, while the characteristic diffraction peaks of the platinum-ruthenium nanomaterials after calcination disappeared, indicating that the calcination treatment transformed the crystalline nanomaterials into an amorphous state.

[0038] Example 2

[0039] (1) In a 25 mL reaction flask, add 20 mg of platinum acetylacetonate, 60 mg of cetyltrimethylammonium chloride and 5 mL of oleylamine in sequence. Stir at room temperature for 20 min and sonicate for 20 min. Add the reducing agent molybdenum hexacarbonyl. Place in an oil bath and react at 180 °C for 3 h.

[0040] (2) Add an oleylamine solution containing 13.7 mg dodecacarbonyltriruthenium to the material obtained in step (1), maintain the temperature at 180°C and continue the reaction for 3 hours. After the reaction is completed, allow it to cool naturally to room temperature.

[0041] (3) The material obtained in step (2) was thoroughly centrifuged and washed several times with a mixture of n-hexane and ethanol (volume ratio 1:1), and then redispersed in n-hexane to obtain a concentration of 2 mg / mL. Pt+Ru Crystalline platinum-ruthenium nanowire dispersion;

[0042] (4) Use a pipette to transfer 0.5 mL of the crystalline platinum-ruthenium nanowire dispersion obtained in step (3), add it to a glass bottle containing 2 mL of activated carbon dispersion (concentration of 2 mg / mL), sonicate at a water temperature of 15-25℃ for 2 h, collect by centrifugation, place it in a vacuum drying oven at 50℃ for 12 h, and finally transfer it to a muffle furnace and calcine it at a rate of 5℃ / min to 200℃ for 2 h in an air atmosphere to obtain ultrafine amorphous platinum-ruthenium nanomaterials.

[0043] The morphology, composition, and crystal structure of the products were systematically studied using modern analytical techniques such as TEM, ICP-MS, and XRD. Figures 1 to 2 As shown in Table 1, TEM characterization revealed a one-dimensional ultrafine nanowire structure. ICP-MS characterization revealed the Pt and Ru content in the product, with a Pt:Ru atomic ratio of 73:27. XRD characterization revealed the crystal phase structure of the carbon-supported platinum-ruthenium nanomaterials before and after calcination in air. The platinum-ruthenium nanomaterials before calcination exhibited characteristic diffraction peaks of the Pt and Ru face-centered cubic phases, while the characteristic diffraction peaks of the platinum-ruthenium nanomaterials after calcination disappeared, indicating that the nanomaterials transformed into an amorphous state after calcination.

[0044] Example 3

[0045] (1) In a 25 mL reaction flask, add 20 mg of platinum acetylacetonate, 60 mg of cetyltrimethylammonium chloride and 5 mL of oleylamine in sequence. Stir at room temperature for 20 min and sonicate for 20 min. Add the reducing agent molybdenum hexacarbonyl. Place in an oil bath and react at 180 °C for 3 h.

[0046] (2) Add an oleylamine solution containing 3.5 mg dodecacarbonyltriruthenium to the material obtained in step (1), maintain the temperature at 180°C and continue the reaction for 3 hours. After the reaction is completed, allow it to cool naturally to room temperature.

[0047] (3) The material obtained in step (2) was thoroughly centrifuged and washed several times with a mixture of n-hexane and ethanol (volume ratio 1:1), and then redispersed in n-hexane to obtain a concentration of 2 mg / mL. Pt+Ru Crystalline platinum-ruthenium nanowire dispersion;

[0048] (4) Use a pipette to transfer 0.5 mL of the crystalline platinum-ruthenium nanowire dispersion obtained in step (3), add it to a glass bottle containing 2 mL of activated carbon dispersion (concentration of 2 mg / mL), sonicate at a water temperature of 15-25℃ for 2 h, collect by centrifugation, place it in a vacuum drying oven at 50℃ for 12 h, and finally transfer it to a muffle furnace and calcine it at a rate of 5℃ / min to 200℃ for 2 h in an air atmosphere to obtain ultrafine amorphous platinum-ruthenium nanomaterials.

[0049] The morphology, composition, and crystal structure of the products were systematically studied using modern analytical techniques such as TEM, ICP-MS, and XRD. Figures 1 to 2 As shown in Table 1, TEM characterization revealed a one-dimensional ultrafine nanowire structure. ICP-MS characterization revealed the Pt and Ru content in the product, with a Pt:Ru atomic ratio of 88:12. XRD characterization revealed the crystal phase structure of the carbon-supported platinum-ruthenium nanomaterials before and after calcination in air. Before calcination, the platinum-ruthenium nanomaterials exhibited characteristic diffraction peaks of the Pt and Ru face-centered cubic phases. After calcination, the characteristic diffraction peaks disappeared, indicating that the crystalline nanomaterials transformed into an amorphous state after calcination.

[0050] Comparative Example 1

[0051] (1) In a 25 mL reaction flask, add 20 mg of platinum acetylacetonate, 60 mg of cetyltrimethylammonium chloride and 5 mL of oleylamine in sequence. Stir at room temperature for 20 min and sonicate for 20 min. Add the reducing agent molybdenum hexacarbonyl. Place in an oil bath and react at 160 °C for 6 h. After the reaction is complete, allow to cool naturally to room temperature.

[0052] (2) The material obtained in step (1) was thoroughly washed several times by centrifugation with a mixture of n-hexane and ethanol (volume ratio 1:1), and then redispersed in n-hexane to obtain a concentration of 2 mg / mL. Pt crystalline pure platinum nanowire dispersion;

[0053] (3) Use a pipette to transfer 0.5 mL of the crystalline pure platinum nanowire dispersion obtained in step (3), add it to a glass bottle containing 2 mL of activated carbon dispersion (concentration of 2 mg / mL), sonicate at a water temperature of 15-25℃ for 2 h, collect by centrifugation, place it in a vacuum drying oven at 50℃ for 12 h, and finally transfer it to a muffle furnace and calcine it at a rate of 5℃ / min to 200℃ for 2 h in an air atmosphere to obtain calcined platinum nanomaterials (calcined-Pt NWs / C).

[0054] The morphology, composition, and crystal structure of the products were systematically studied using modern analytical techniques such as TEM, ICP-MS, and XRD. Figures 1 to 2 As shown in Table 1, TEM characterization revealed a one-dimensional ultrafine nanowire structure. ICP-MS characterized the Pt and Ru content in the product, with the product containing only Pt. XRD characterized the crystal phase structure of the carbon-supported platinum nanomaterial before and after calcination in air. Compared to the platinum nanomaterial before calcination, the characteristic diffraction peaks of the calcined platinum nanomaterial had narrower peak widths and stronger peak intensities, indicating that the crystallinity of the calcined platinum nanomaterial was improved.

[0055] Table 1. ICP-MS results of ultrafine platinum-ruthenium nanomaterials with different ruthenium contents prepared in Examples 1 to 3 and Comparative Example 1.

[0056]

[0057] This invention explores the application of the synthesized ultrafine amorphous platinum-ruthenium nanomaterial catalyst in alkaline hydrogen oxidation electrocatalysis. The catalytic activity of the ultrafine amorphous platinum-ruthenium nanomaterial catalyst and the crystalline nanomaterial catalyst (carbon-supported, uncalcined platinum-ruthenium nanomaterials) prepared in Example 1 in the alkaline hydrogen oxidation electrocatalysis process is compared with that of commercial platinum-ruthenium catalysts and commercial platinum catalysts. The results are as follows: Figure 4 As shown, the ultrafine amorphous platinum-ruthenium nanomaterials prepared in this invention exhibit significantly enhanced catalytic activity for hydroxide oxidation.

[0058] This invention investigates the CO tolerance of the synthesized ultrafine amorphous platinum-ruthenium nanomaterial catalyst in alkaline hydroxide electrocatalysis. The ultrafine amorphous platinum-ruthenium nanomaterial catalyst and the crystalline nanomaterial catalyst (carbon-supported, uncalcined platinum-ruthenium nanomaterials) prepared in Example 1 are compared with commercial platinum-ruthenium catalysts and commercial platinum catalysts using a chronoamperometry method at a constant potential of 50 mV. The results are as follows: Figure 5 As shown, the CO tolerance of the ultrafine amorphous platinum-ruthenium nanomaterials prepared in this invention is significantly improved.

[0059] The above Figure 4 The test conditions were as follows: freshly prepared 0.1M potassium hydroxide solution saturated with H2, a three-electrode system was used, in which a carbon rod was used as the counter electrode, a mercury / mercury oxide electrode was used as the reference electrode, and a rotating disk electrode with a carbon-supported catalyst was used as the working electrode, and linear voltammetry was performed.

[0060] The above Figure 5 The test conditions were as follows: a freshly prepared 1000ppm CO / H2 saturated 0.1M potassium hydroxide solution was used. A three-electrode system was employed, with a carbon rod as the counter electrode, a mercury / mercury oxide electrode as the reference electrode, and a rotating disk electrode with a carbon-supported catalyst as the working electrode. The test was conducted using the chronoamperometry method at a rotation speed of 2000rpm and a potential of 50mV.

[0061] Before electrochemical testing, the nanocatalyst film uniformly spread on the rotating disk electrode was placed in a 0.1M perchloric acid solution saturated with N2 and subjected to cyclic voltammetry to activate the electrode surface.

[0062] The above description is merely a preferred embodiment of the present invention, and therefore should not be construed as limiting the scope of the present invention. All equivalent changes and modifications made in accordance with the scope of the patent and the contents of the specification should still fall within the scope of the present invention.

Claims

1. A method for preparing ultrafine amorphous platinum-ruthenium nanomaterials, characterized in that: Includes the following steps: (1) After thoroughly mixing acetylacetonate platinum, hexadecyltrimethylammonium chloride and oleylamine at room temperature, add hexacarbonyl molybdenum and react at 160-200℃ for 1-4 hours; (2) Under heat preservation conditions, add oleylamine solution of dodecyltriruthenium carbonyl to the material obtained in step (1), continue the heat preservation reaction for 1-4 hours, and then cool naturally to room temperature; (3) Wash the material obtained in step (2) thoroughly with a mixture of ethanol and n-hexane, then centrifuge and redisperse it in n-hexane to obtain a crystalline platinum-ruthenium nanowire dispersion. (4) Add the platinum-ruthenium nanowire dispersion obtained in step (3) to the activated carbon dispersion, sonicate at 15-25℃ for 1-3 hours, then centrifuge to collect the precipitate, and then vacuum dry and calcine in air to obtain the ultrafine amorphous platinum-ruthenium nanomaterial.

2. The preparation method according to claim 1, characterized in that: In step (1), the ratio of acetylacetonate platinum, hexadecyltrimethylammonium chloride, hexacarbonylmolybdenum and oleylamine is 15-25mg:50-70mg:25-35mg:4-6mL.

3. The preparation method according to claim 2, characterized in that: In the oleylamine solution of dodecyltriruthenium carbonyl in step (2), the ratio of dodecyltriruthenium carbonyl to oleylamine is 2-22 mg: 1-3 mL.

4. The preparation method according to claim 3, characterized in that: The mass ratio of the platinum acetylacetonate to the ruthenium dodecylcarbonyl is 15-25:2-22.

5. The preparation method according to claim 4, characterized in that: In step (4), the volume ratio of the platinum-ruthenium nanowire dispersion to the activated carbon dispersion is 0.3-0.7:1-3, and the concentration of activated carbon in the activated carbon dispersion is 1-3 mg / mL.

6. The preparation method according to any one of claims 1 to 5, characterized in that: The vacuum drying temperature is 40-60℃, and the time is 8-15 hours.

7. The preparation method according to any one of claims 1 to 5, characterized in that: The calcination temperature in the air is 180-220℃, and the time is 1-3 hours.

8. The application of the ultrafine amorphous platinum-ruthenium nanomaterials prepared by the preparation method according to any one of claims 1 to 7 in the preparation of alkaline hydroxide reaction catalysts.

9. A basic hydrogenation reaction catalyst, characterized in that: The raw materials include ultrafine amorphous platinum-ruthenium nanomaterials prepared by the preparation method described in any one of claims 1 to 7.

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