A ternary composite catalyst of ruthenium, tellurium and selenium, and its preparation method and application

Abstract

This invention discloses a ruthenium-tellurium-selenium ternary composite catalyst, its preparation method, and its application. The ruthenium-tellurium-selenium ternary composite catalyst comprises a carbon support and RuTe supported thereon. x Se y Nanoparticles, where x represents the molar ratio of tellurium to ruthenium, y represents the molar ratio of selenium to ruthenium, and the sum of x and y is 1; the nanoparticles comprise a composite crystalline phase of orthorhombic RuTe2 and cubic RuSe2. The catalyst RuTe x Se y After heat treatment at 300~500℃, / C forms a RuTe2-RuSe2 composite crystal phase. The atomic ratio is precisely controlled through the Te-Se dichalcogenide synergistic strategy, which optimizes the adsorption capacity of oxygen-containing intermediates in the OER / ORR process. The introduction of Se effectively inhibits particle growth and increases the active specific surface area, while avoiding the problems of active site coverage and agglomeration caused by excessive Se. This increases the ORR half-wave potential to 0.71V, achieving 57.5% of the performance of commercial Pt / C catalysts, while reducing costs by 60~70%. It demonstrates high efficiency and low cost advantages in water electrolysis, metal-air batteries, and fuel cells.

Description

Technical Field

[0001] This invention relates to the field of electrochemical catalysis technology, and more specifically, to a ruthenium-tellurium-selenium ternary composite catalyst, its preparation method, and its application. Background Technology

[0002] With the increasing urgency of global energy structure transformation and environmental protection, the development of efficient and stable electrochemical energy conversion technologies has become a key research focus. The oxygen reduction reaction (ORR) and oxygen evolution reaction (OER), as core electrochemical processes in clean energy technologies such as fuel cells and water electrolysis for hydrogen production, suffer from slow reaction kinetics and high overpotentials that severely limit the performance improvement of related equipment. However, existing noble metal catalyst systems face numerous challenges, necessitating the development of novel, highly efficient catalysts to overcome these technological bottlenecks.

[0003] In the field of OER catalysis, oxides of noble metals iridium (Ir) and ruthenium (Ru) (IrO2 and RuO2) are currently commonly used high-efficiency catalysts. While IrO2 exhibits excellent catalytic activity, its scarcity and extremely high cost make it difficult to meet the demands of large-scale industrial applications. In contrast, although RuO2 is relatively inexpensive, it is prone to corrosion under strongly alkaline conditions, leading to deactivation of active sites and significantly insufficient stability. These issues limit the practical application of existing Ru-based OER catalysts.

[0004] In the field of ORR catalysis, platinum (Pt) is currently the primary catalyst. However, Pt catalysts suffer from high cost, limited resources, and insufficient durability, hindering their commercial application in hydrogen fuel cells. Ruthenium (Ru), the cheapest of the Pt group metals, costs only 30%–50% of Pt, making ruthenium-based catalysts a promising alternative. Studies have shown that introducing sulfur (S) to form ruthenium-based dichalcogenides can significantly enhance ORR activity. Existing technologies, such as Chinese invention patent (CN111939940B), disclose a ruthenium-based catalyst and its preparation method. This technology improves catalyst particle dispersion by loading ruthenium-based dichalcogenides onto a carbon support and avoids particle agglomeration during high-temperature processing through the porous structure of the carbon support. However, this technology still fails to fundamentally solve the problem of catalyst stability under harsh conditions; stability under strongly acidic (e.g., proton exchange membrane fuel cell environments) and strongly alkaline (e.g., water electrolysis environments) conditions needs further improvement.

[0005] Therefore, developing a novel ruthenium-based catalyst that combines excellent OER and ORR activity with good stability has significant application value. Summary of the Invention

[0006] Based on this, it is necessary to address the above-mentioned technical problems by providing a ruthenium-tellurium-selenium ternary composite catalyst, its preparation method, and its application. Compared with traditional platinum / iridium-based catalysts, the ruthenium, tellurium, and selenium elements used in this invention are more abundant and cheaper, and the preparation process does not require complex equipment or high-energy-consuming processes, which meets the requirements of green industrial production.

[0007] To address the aforementioned technical problems, the first aspect of this invention provides a ruthenium telluride selenium ternary composite catalyst, comprising a carbon support and RuTe supported thereon. x Se y Nanoparticles, wherein x represents the molar ratio of tellurium to ruthenium, y represents the molar ratio of selenium to ruthenium, and the sum of x and y is 1; the nanoparticles contain a composite crystalline phase of orthorhombic RuTe2 and cubic RuSe2.

[0008] Furthermore, the average particle size of the nanoparticles is less than 5 nm, the value of x ranges from 0.2 to 0.8, and the value of y ranges from 0.2 to 0.8.

[0009] Furthermore, the RuTe x Se y The value of x for the nanoparticles is 0.8, and the value of y is 0.2.

[0010] The second aspect of this invention provides a method for preparing the above-mentioned ruthenium tellurium selenide ternary composite catalyst, which includes the following steps: S1, mixing ruthenium trichloride hydrate RuCl3·xH2O, sodium tellurite Na2TeO3, selenium dioxide SeO2 and a carbon support in ethylene glycol; S2, microwave-assisted synthesis; S3, heat treatment at 300~500℃ under an inert atmosphere to obtain the ruthenium tellurium selenide ternary composite catalyst.

[0011] Furthermore, in step S1, ruthenium trichloride hydrate RuCl3·xH2O, sodium tellurite Na2TeO3, selenium dioxide SeO2, and carbon support are mixed in ethylene glycol at a molar ratio of ruthenium, tellurium, and selenium of 1:(0.2~0.8):(0.2~0.8), and the mass ratio of ruthenium trichloride hydrate RuCl3·xH2O to carbon support is 1:1~1.2.

[0012] Furthermore, the microwave-assisted synthesis in step S2 has a power of 700-900W and a reaction time of 2-4 minutes.

[0013] Furthermore, the heat treatment involves heating the temperature to 300-500°C at a rate of 5°C / min under an inert atmosphere and holding it at that temperature for 2 hours.

[0014] Furthermore, the product is washed sequentially with anhydrous ethanol and deionized water before being vacuum dried prior to the heat treatment.

[0015] Furthermore, the microwave-assisted synthesis in step S2 has a power of 800W and a reaction time of 3 minutes; the heat treatment is carried out in an inert atmosphere at a heating rate of 5℃ / min to 400℃ and held for 2 hours.

[0016] The third aspect of this invention proposes the ruthenium-tellurium-selenium ternary composite catalyst RuTe x Se y / C Applications in water electrolysis, metal-air batteries, or fuel cells.

[0017] Compared with the prior art, the present invention has the following beneficial effects:

[0018] The ruthenium-tellurium-selenium ternary composite catalyst RuTe provided by this invention x Se y / C and its preparation methods and applications, RuTe ternary composite catalyst x Se y A RuTe2-RuSe2 dual-active-site structure was constructed via microwave-assisted synthesis. Utilizing the reducing power of ethylene glycol and the efficient heating properties of microwaves, the reduction of the Ru precursor and the alloying of Te / Se were completed within 3-5 minutes, forming uniformly dispersed nanoparticles. This preparation process is simple, efficient, energy-saving, and suitable for large-scale production. The catalyst RuTe2... x Se y After heat treatment at 300~500℃, / C forms a RuTe2-RuSe2 composite crystal phase. The atomic ratio is precisely controlled through the Te-Se dichalcogenide synergistic strategy, which optimizes the adsorption capacity of oxygen-containing intermediates in the OER / ORR process. The introduction of Se effectively inhibits particle growth and increases the active specific surface area, while avoiding the problems of active site coverage and agglomeration caused by excessive Se. This increases the ORR half-wave potential to 0.71V, achieving 57.5% of the performance of commercial Pt / C catalysts, while reducing costs by 60~70%. It demonstrates high efficiency and low cost advantages in water electrolysis, metal-air batteries, and fuel cells. Attached Figure Description

[0019] To more clearly illustrate the solutions in this application or the prior art, the drawings used in the description of the embodiments or the prior art will be briefly introduced below. Obviously, the drawings described below are some embodiments of this application. For those skilled in the art, other drawings can be obtained from these drawings without creative effort.

[0020] Figure 1A RuTe of Example 1 0.8 Se 0.2 TEM morphology of the / C catalyst;

[0021] Figure 1B RuTe of Example 10.8 Se 0.2 Nanoparticle size distribution of / C catalyst;

[0022] Figure 1C RuTe of Example 1 0.8 Se 0.2 HRTEM lattice fringes of / C catalyst;

[0023] Figure 1D RuTe of Example 1 0.8 Se 0.2 EDS energy spectrum of / C catalyst;

[0024] Figure 1E RuTe for Example 2 0.6 Se 0.4 TEM morphology of the / C catalyst;

[0025] Figure 1F RuTe for Example 2 0.6 Se 0.4 Nanoparticle size distribution of / C catalyst;

[0026] Figure 1G RuTe for Example 3 0.4 Se 0.6 TEM morphology of the / C catalyst;

[0027] Figure 1H RuTe for Example 3 0.4 Se 0.6 Nanoparticle size distribution of / C catalyst;

[0028] Figure 1I RuTe for Example 4 0.2 Se 0.8 TEM morphology of the / C catalyst;

[0029] Figure 1J RuTe for Example 4 0.2 Se 0.8 Nanoparticle size distribution of / C catalyst;

[0030] Figure 2A The image shows the TEM morphology of the RuSe / C catalyst obtained in Comparative Example 1.

[0031] Figure 2B The image shows the TEM morphology of the RuTe / C catalyst obtained in Comparative Example 2.

[0032] Figure 3 To verify the ORR polarization curves of the catalysts in Examples 1-4 and Comparative Examples 1-2 in Example 1;

[0033] Figure 4 To verify the XRD patterns of the catalysts in Example 1 and Comparative Examples 1-2 in Example 2;

[0034] Figure 5 To verify the different heat treatment temperatures of RuTe in Example 3 0.8 Se 0.2 ORR polarization curves of / C catalyst;

[0035] Figure 6 To verify Example 4 RuTe 0.8 Se 0.2 Comparison of OER polarization curves between / C and commercial RuO2 catalysts;

[0036] Figure 7 To verify the battery polarization curves of different cathode catalysts in Example 5;

[0037] Figure 8 To verify Example 6 RuTe 0.8 Se 0.2 Performance comparison of / C catalyst before and after 1000 cycles;

[0038] Figure 9 To verify Example 6 RuTe 0.8 Se 0.2 HAADF-STEM image of the / C catalyst after 1000 cycles. Detailed Implementation

[0039] To enable those skilled in the art to better understand the present invention, the technical solutions in the embodiments of the present invention will be clearly and completely described below. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort should fall within the scope of protection of the present invention.

[0040] To enable those skilled in the art to better understand the present application, the technical solutions in the embodiments of the present application will be clearly and completely described below.

[0041] Description of instruments and chemical reagents used in the embodiments of this invention

[0042] Table 1. List of instruments and equipment used in the embodiments of the present invention

[0043]

[0044] Table 2 List of chemical reagents used in the embodiments of the present invention

[0045]

[0046] In the embodiments of this invention, the ruthenium loading in the ruthenium-tellurium-selenium ternary composite catalyst is based on the total mass of the catalyst (including the mass of ruthenium, tellurium, selenium, and carbon support), with a designed theoretical ruthenium loading of 20.0 wt%. The loading is controlled by adjusting the mass ratio of RuCl3•xH2O (x=1~3) to the carbon support. In each embodiment, the amount of Te and Se introduced is adjusted based on their molar ratio with Ru, while maintaining a constant theoretical Ru loading.

[0047] Example 1

[0048] This embodiment provides a ruthenium telluride selenium ternary composite catalyst RuTe x Se y The preparation method of / C includes the following steps:

[0049] S1. Raw material preparation and mixing: Place 50 mL of ethylene glycol in a 100 mL beaker, add 57.3 mg of carbon black as a carrier material, and stir at 800 rpm for 30 minutes on a magnetic stirrer until completely dispersed. Then, according to the molar ratio of ruthenium (Ru), tellurium (Te), and selenium (Se) of 1:0.8:0.2, add 54.6 mg of ruthenium trichloride (RuCl3•xH2O), 35.5 mg of sodium tellurite (Na2TeO3), and 4.5 mg of selenium dioxide (SeO2) in sequence.

[0050] S2. Precursor Treatment: The above mixed solution was placed in an ultrasonic cleaner and ultrasonically treated in a water bath at a frequency of 40 kHz for 30 minutes to ensure thorough mixing of all components. Then, the beaker was placed in a microwave oven with a power setting of 800W and a reaction time of 3 minutes for microwave-assisted synthesis. This step utilizes the reducing properties of ethylene glycol and the rapid, uniform heating characteristics of microwaves to complete the precursor reduction and alloying in a very short time, avoiding the long reaction time required by traditional hydrothermal methods and improving preparation efficiency.

[0051] S3. Post-treatment: After the reaction is complete, the product is naturally cooled to room temperature (25±2℃), filtered using a Buchner funnel, and washed three times each with anhydrous ethanol and deionized water, 50 mL each time. The resulting solid product is transferred to a vacuum drying oven and dried at 65℃ for 12 hours.

[0052] S4. Heat Treatment: The dried sample was placed in a quartz boat in a tubular furnace, and an inert gas was introduced. In this embodiment, high-purity nitrogen (99.999%) was used as the protective gas. The temperature was raised to 400°C at a rate of 5°C / min, held at that temperature for 2 hours, and then cooled to room temperature with the furnace. The target product, ruthenium tellurium selenide composite catalyst, denoted as RuTe, was finally obtained. 0.8 Se 0.2 / C, where x=0.8 and y=0.2 represent the molar ratios of Te, Se, and Ru, respectively. The heat treatment process in this step not only removes residual organic matter from the surface but also induces the formation of RuTe2 and RuSe2 crystalline phases, while simultaneously enhancing the bonding force between the nanoparticles and the carbon support, thus improving stability.

[0053] The obtained RuTe 0.8 Se 0.2 The / C composite catalyst was characterized by transmission electron microscopy (TEM) and energy dispersive spectroscopy (EDS), and the results are as follows: Figures 1A-1D As shown. By Figure 1A The transmission electron microscope image shows that RuTe 0.8 Se 0.2 The nanoparticles were uniformly distributed on the carbon support surface, and no obvious aggregation was observed. Figure 1B The display showed that 100 randomly selected nanoparticles were statistically analyzed, and the average particle size was measured to be 4.1 nm; Figure 1C High-resolution TEM images show that the interplanar spacings of 0.286 nm and 0.265 nm correspond to the (111) crystal plane of the orthorhombic phase RuTe2 and the (210) crystal plane of the cubic phase RuSe2, respectively, confirming the formation of a dual-active-site structure in the material. Figure 1D EDS analysis confirmed that the catalyst mainly contains C, O, Se, Ru and Te elements, with the molar ratio of Ru, Te and Se being 2.6:2.5:1.1.

[0054] Example 2

[0055] This embodiment provides a ruthenium telluride selenium ternary composite catalyst RuTe x Se y The preparation method of / C differs from that of Example 1 in that the molar ratio of each raw material is adjusted to Ru:Te:Se = 1:0.6:0.4. The specific steps include: S1, taking 50 mL of ethylene glycol in a beaker, adding 59.2 mg of carbon black, dispersing it with magnetic stirring, and then sequentially adding 54.6 mg of RuCl3•xH2O, 26.6 mg of Na2TeO3 and 9.0 mg of SeO2; S2, after ultrasonic treatment in a water bath for 30 minutes, reacting with microwave at 700 W for 4 minutes, washing the product with ethanol / deionized water and then vacuum drying at 60 °C for 14 hours; S3, heat-treating at 400 °C for 2 hours under a nitrogen atmosphere to finally obtain the target product, ruthenium tellurium selenide composite catalyst, denoted as RuTe. 0.6 Se 0.4 / C.

[0056] Example 3

[0057] This embodiment provides a ruthenium telluride selenium ternary composite catalyst RuTe x Se yThe preparation method of / C differs from that of Example 1 in that the molar ratio of each raw material is Ru:Te:Se = 1:0.4:0.6. Specifically, in step S1, 61.2 mg of carbon black, 54.6 mg of RuCl3•xH2O, 17.7 mg of Na2TeO3, and 13.5 mg of SeO2 are added; in step S2, after ultrasonic treatment in a water bath for 30 minutes, the product is microwaved at 900 W for 2 minutes, washed with ethanol / deionized water, and then vacuum dried at 70°C for 10 hours. Subsequent processing is the same as in Example 1, ultimately yielding the target product, the ruthenium tellurium selenide composite catalyst, denoted as RuTe. 0.4 Se 0.6 / C.

[0058] Example 4

[0059] This embodiment provides a ruthenium telluride selenium ternary composite catalyst RuTe x Se y The preparation method of / C differs from that of Example 1 in that the molar ratio of each raw material is Ru:Te:Se = 1:0.2:0.8. Specifically, in step S1, 63.1 mg of carbon black, 54.6 mg of RuCl3•xH2O, 8.9 mg of Na2TeO3, and 17.9 mg of SeO2 are added. The subsequent treatment is the same as in Example 1, and the target product, ruthenium tellurium selenide composite catalyst, is finally obtained, denoted as RuTe. 0.2 Se 0.8 / C.

[0060] The catalyst nanoparticles obtained in Examples 2-4 were subjected to transmission electron microscopy (TEM) and their particle size was statistically analyzed. The results are as follows: Figures 1E to 1J As shown; all three-way catalysts (RuTe) X Se y The active metal nanoparticles of / C) all exhibited a uniform dispersion without obvious agglomeration, with a particle size distribution in the range of 3-5 nm, similar to those in Example 1 (RuTe). 0.8 Se 0.2 The trend of Te / C is consistent, proving that Te / Se co-doping has universality in controlling the size of Ru nanoparticles.

[0061] Comparative Example 1

[0062] This comparative example provides a method for preparing a ruthenium selenide binary catalyst RuSe / C, which differs from Example 1 in that only Ru and Se precursors are used, and the molar ratio of Ru to Se is 1:1. The specific steps are as follows: S1, 50 mL of ethylene glycol is placed in a beaker, 65.1 mg of carbon black is added, and after magnetic stirring and dispersion, 54.6 mg of RuCl3•xH2O and 22.4 mg of SeO2 are added sequentially (Na2TeO3 is not added); S2~S4 are the same as in Example 1, and finally the RuSe / C catalyst is obtained.

[0063] Comparative Example 2

[0064] This comparative example provides a method for preparing a ruthenium-tellurium binary catalyst (RuTe / C), which differs from Example 1 in that only Ru and Te precursors are used, with a Ru to Te molar ratio of 1:1. The specific preparation steps are as follows: S1, 50 mL of ethylene glycol is placed in a beaker, 55.3 mg of carbon black is added, and after magnetic stirring and dispersion, 54.6 mg of RuCl3•xH2O and 44.4 mg of Na2TeO3 (without adding SeO2) are added sequentially; S2~S4 are the same as in Example 1, and finally the RuTe / C catalyst is obtained.

[0065] Comparative Example 3

[0066] This comparative example provides a method for preparing a ruthenium monometallic catalyst (Ru / C), which differs from Example 1 only in that: no Te and Se precursors are added, and only RuCl3•xH2O is used as the metal source. The specific adjustments are as follows: S1, 50 mL of ethylene glycol is placed in a beaker, 81.9 mg of carbon black (corresponding to a 20 wt% Ru loading) is added, and after magnetic stirring and dispersion, only 54.6 mg of RuCl3•xH2O is added (without adding Na2TeO3 and SeO2); Steps S2 to S4 are the same as in Example 1, and finally the Ru / C catalyst is obtained.

[0067] The RuTe / C and RuSe / C catalysts obtained in Comparative Examples 1 and 2 were characterized by transmission electron microscopy (TEM), and the results are as follows: Figures 2A-2B As shown, the RuTe / C and RuSe / C catalysts exhibit poor uniformity in nanoparticle distribution.

[0068] To more intuitively demonstrate the differences in raw material composition between Examples 1-4 and Comparative Examples 1-3, Table 3 lists the molar ratios of Ru, Te, and Se in different catalysts and the corresponding amounts of raw materials.

[0069] Table 3: Molar ratio of catalyst and amount of raw materials used in Examples 1-4 and Comparative Examples 1-2

[0070]

[0071] Comparative Example 4

[0072] This comparative example provides a ruthenium tellurium selenide ternary composite catalyst RuTe x Se y The preparation method of / C differs from that of Example 1 only in that the heat treatment temperature in step S4 is adjusted to 300℃ (other conditions are the same), ultimately obtaining RuTe heat-treated at 300℃. 0.8 Se 0.2 / C catalyst.

[0073] Comparative Example 5

[0074] This comparative example provides a ruthenium tellurium selenide ternary composite catalyst RuTe x Se y The preparation method of / C differs from that of Example 1 only in that the heat treatment temperature in step S4 is adjusted to 500℃ (other conditions are the same), ultimately obtaining RuTe heat-treated at 500℃. 0.8 Se 0.2 / C catalyst.

[0075] Comparative Example 6

[0076] This comparative example provides a ruthenium tellurium selenide ternary composite catalyst RuTe x Se y The preparation method of / C differs from that of Example 1 only in that step S4 heat treatment is omitted (only drying is performed), ultimately yielding untreated RuTe. 0.8 Se 0.2 / C catalyst.

[0077] Verification Example 1

[0078] This verification example tests the oxygen reduction reaction (ORR) performance of the composite catalysts prepared in Examples 1-4 and Comparative Examples 1-2. The test conditions are: oxygen-saturated 0.1 mol / L HClO4 solution, room temperature, and polarization curves are measured using the rotating disk electrode method. The test results are as follows: Figure 3 As shown, the half-wave potential (E) of each catalyst was obtained through testing and analysis. 1 / 2 The following are respectively: RuTe 0.8 Se 0.2 / C catalyst 0.71V, RuTe 0.6 Se 0.4 / C catalyst 0.70V, RuTe 0.4 Se 0.6 / C catalyst 0.69V, RuTe 0.2 Se 0.8 / C catalyst 0.66V, RuSe / C catalyst 0.63V, RuTe / C catalyst 0.66V. The results show that the RuTe prepared in Example 1... 0.8 Se 0.2 The / C catalyst exhibited the best ORR catalytic activity, with its half-wave potential increasing by 80 mV and 50 mV compared to the single-component RuSe / C and RuTe / C of Comparative Examples 1 and 2, respectively. This fully demonstrates that constructing RuTe2 and RuSe2 composite active sites can significantly improve the oxygen reduction performance of the catalyst.

[0079] Verification Example 2

[0080] In this verification example, X-ray diffraction (XRD) was used to characterize the catalysts prepared in Example 1 and Comparative Examples 1-2. The results are as follows: Figure 4 The spectra show that the main phase structure of the RuTe / C catalyst is orthorhombic RuTe2, while the main phase structure of the RuSe / C catalyst is cubic RuSe2. 0.8 Se 0.2 The / C catalyst simultaneously exhibited orthorhombic RuTe2 and cubic RuSe2 crystallization peaks, confirming the formation of a RuTe2 and RuSe2 dual-active-site structure. The introduction of Se reduced the crystallinity, leading to RuTe2 crystallinity... 0.8 Se 0.2 The crystallinity of the / C catalyst is significantly lower than that of the RuTe / C catalyst.

[0081] Verification Example 3

[0082] This verification example uses the rotating disk electrode method to verify the effect of heat treatment temperature on RuTe. 0.8 Se 0.2 The effect of / C catalyst ORR performance, RuTe synthesized at different heat treatment temperatures in Examples 1 and Comparative Examples 4-6 0.8 Se 0.2 The ORR polarization curve of the / C catalyst was tested under oxygen saturation of 0.1 mol / L HClO4, and the results are as follows: Figure 5 As shown in the figure. The test results show that the half-wave potential of the catalyst in Comparative Example 6 (None) without heat treatment is 0.66V; after heat treatment, the half-wave potentials of Comparative Example 4 (300℃), Example 1 (400℃), and Comparative Example 5 (500℃) increased to 0.68V, 0.71V, and 0.67V, respectively. Among them, the sample of Example 1 heat-treated at 400℃ showed the best catalytic activity, which was 50mV higher than that of the untreated sample of Comparative Example 5, confirming the controllable adjustment of the heat treatment temperature on the catalyst performance.

[0083] Verification Example 4

[0084] This verification example uses an electrochemical workstation to test the RuTe prepared in Example 1. 0.8 Se 0.2 The OER polarization curves of the / C catalyst under 1.0 mol / L KOH conditions were compared with those of the common commercial catalyst RuO2. The results are as follows: Figure 6 As shown. By Figure 6 It can be seen that when the driving current density is 10mA / cm 2 At that time, RuTe 0.8 Se 0.2 The required external overpotential for the / C catalyst is 273mV, which is about 27mV lower than the 300mV required for commercial RuO2, indicating that RuTe 0.8 Se 0.2The / C catalyst exhibits excellent water electrolysis catalytic activity, further demonstrating that the synergistic effect of the Te-Se dual elements optimizes the electronic structure of the Ru active sites, thereby improving catalytic efficiency.

[0085] Verification Example 5

[0086] This verification example uses a fuel cell testing system to test the RuTe fuel cell from Example 1. 0.8 Se 0.2 Performance tests of hydrogen / oxygen proton exchange membrane fuel cells were conducted using RuTe / C (Comparative Example 2), Ru / C (Comparative Example 3), and commercially available Pt / C as cathode catalysts. The tests were performed at a constant temperature of 80℃. The inlet flow rates of pure hydrogen (200 mL / min) and pure oxygen (400 mL / min) were precisely controlled using a mass flow controller. The cathode metal loading was 0.2 mg·cm³. -2 The back pressure is controlled at 50 kPa, and a single cell is assembled using an NF211 proton exchange membrane. Figure 7 The polarization and power density curves of the tests are shown. The results show that RuTe 0.8 Se 0.2 The maximum power density of the / C catalyst reaches 802 mW / cm². 2 Compared to RuTe / C's 641mW / cm 2 462mW / cm of Ru / C 2 And the best Ru-based catalyst reported in the literature is 672 mW / cm 2 All showed significant improvements, reaching 1395 mW / cm² for commercial Pt / C catalysts. 2 Ru accounts for 57.5% of the total, and it is the cheapest platinum group metal, with its price only 30% to 50% of Pt, giving it a significant cost advantage. RuTe 0.8 Se 0.2 / C catalysts show promising prospects for commercial application.

[0087] Verification Example 6

[0088] This verification example validates RuTe through accelerated aging testing. 0.8 Se 0.2 The stability of the / C catalyst was specifically assessed by cycling the catalyst 1000 times in an oxygen-saturated 0.1M HClO4 solution at a potential of 0.05–0.90 V (vs. RHE) at a scan rate of 50 mV / s. The results are as follows: Figure 8 As shown, RuTe 0.8 Se 0.2 / C catalyst oxygen reduction half-wave potential (E 1 / 2The catalyst exhibits excellent stability with a degradation of only 30 mV, representing a degradation rate of 4.5%, indicating that it maintains good activity during long-term operation. The RuTe catalyst, after undergoing 1000 cycles of stability testing... 0.8 Se 0.2 The / C catalyst was subjected to STEM-EDS elemental analysis, and the results are as follows: Figure 9 As shown, RuTe 0.8 Se 0.2 The metal nanoparticles (bright areas) in the / C catalyst remain well dispersed, consistent with its excellent electrochemical stability.

[0089] Through the above-mentioned systematic verification, the ruthenium-tellurium-selenium ternary composite catalyst of the present invention, through the synergistic effect of the RuTe2 and RuSe2 dual-active-site structure and optimized nanoparticle dispersion, exhibits excellent catalytic activity and stability in oxygen reduction reaction (ORR), oxygen evolution reaction (OER), and fuel cell applications. As a highly efficient bifunctional electrocatalyst, the ruthenium-tellurium-selenium ternary composite catalyst of the present invention is particularly suitable for oxygen evolution anodes and / or hydrogen evolution cathodes in water electrolysis devices, air electrodes in metal-air batteries, and cathode catalysts in fuel cells. It can significantly improve the overall efficiency of energy conversion equipment and has significant advantages in practical applications.

[0090] Obviously, the embodiments described above are only some embodiments of this application, not all embodiments. The accompanying drawings show preferred embodiments of this application, but do not limit the patent scope of this application. This application can be implemented in many different forms; rather, the purpose of providing these embodiments is to provide a more thorough and comprehensive understanding of the disclosure of this application. Although this application has been described in detail with reference to the foregoing embodiments, those skilled in the art can still modify the technical solutions described in the foregoing specific embodiments, or make equivalent substitutions for some of the technical features. Any equivalent structures made using the content of this application's specification and drawings, directly or indirectly applied to other related technical fields, are similarly within the scope of patent protection of this application.

Claims

1. A ruthenium-tellurium-selenium ternary composite catalyst, characterized in that, Including carbon supports and RuTe supported on carbon supports x Se y Nanoparticles, wherein x represents the molar ratio of tellurium to ruthenium, y represents the molar ratio of selenium to ruthenium, and the sum of x and y is 1; the nanoparticles contain a composite crystalline phase of orthorhombic RuTe2 and cubic RuSe2; The preparation method of the ruthenium-tellurium-selenium ternary composite catalyst includes the following steps: S1, mixing ruthenium trichloride hydrate RuCl3·xH2O, sodium tellurite Na2TeO3, selenium dioxide SeO2 and carbon support in ethylene glycol at a molar ratio of ruthenium, tellurium and selenium of 1:(0.2~0.8):(0.2~0.8); S2, microwave-assisted synthesis; S3, heat treatment under an inert atmosphere to obtain the ruthenium-tellurium-selenium ternary composite catalyst.

2. The ruthenium-tellurium-selenium ternary composite catalyst according to claim 1, characterized in that, The average particle size of the nanoparticles is less than 5 nm, the value of x ranges from 0.2 to 0.8, and the value of y ranges from 0.2 to 0.

8.

3. The ruthenium-tellurium-selenium ternary composite catalyst according to claim 2, characterized in that, The RuTe x Se y The value of x for the nanoparticles is 0.8, and the value of y is 0.

2.

4. A method for preparing the ruthenium-tellurium-selenium ternary composite catalyst according to claim 1, characterized in that, Includes the following steps: S1. Ruthenium trichloride hydrate RuCl3·xH2O, sodium tellurite Na2TeO3, selenium dioxide SeO2, and carbon support are mixed in ethylene glycol; S2. Microwave-assisted synthesis; S3. After heat treatment at 300~500℃ under an inert atmosphere, a ruthenium-tellurium-selenium ternary composite catalyst is obtained.

5. The preparation method of the ruthenium-tellurium-selenium ternary composite catalyst according to claim 4, characterized in that, In step S1, ruthenium trichloride hydrate RuCl3·xH2O, sodium tellurite Na2TeO3, selenium dioxide SeO2, and carbon support are mixed in ethylene glycol at a molar ratio of ruthenium, tellurium, and selenium of 1:(0.2~0.8):(0.2~0.8), and the mass ratio of ruthenium trichloride hydrate RuCl3·xH2O to carbon support is 1:1~1.

2.

6. The preparation method of the ruthenium-tellurium-selenium ternary composite catalyst according to claim 5, characterized in that, The microwave-assisted synthesis in step S2 has a power of 700-900W and a reaction time of 2-4 minutes.

7. The method for preparing the ruthenium-tellurium-selenium ternary composite catalyst according to claim 5, characterized in that, The heat treatment involves heating the temperature to 300-500°C at a rate of 5°C / min under an inert atmosphere and holding it at that temperature for 2 hours.

8. The preparation method of the ruthenium-tellurium-selenium ternary composite catalyst according to claim 5, characterized in that, Before the heat treatment, the sample was washed with anhydrous ethanol and deionized water in sequence, followed by vacuum drying.

9. The preparation method of the ruthenium-tellurium-selenium ternary composite catalyst according to claim 7, characterized in that, The microwave-assisted synthesis in step S2 has a power of 800W and a reaction time of 3 minutes; the heat treatment is carried out in an inert atmosphere at a heating rate of 5℃ / min to 400℃ and held for 2 hours.

10. The application of the ruthenium telluride selenium ternary composite catalyst according to any one of claims 1 to 3 in water electrolysis, metal-air batteries or fuel cells.

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