Heterostructured tetrahedral palladium-indium-molybdenum nanocatalyst, synthesis method and application thereof

Abstract

The application discloses a kind of polyphase structure tetrahedral palladium indium molybdenum nanometer catalyst and synthesis method and application thereof, take palladium precursor, acetylacetone indium and hexacarbonyl molybdenum;Palladium precursor, acetylacetone indium and hexacarbonyl molybdenum are dispersed in DMF, and uniform mixed solution is obtained by ultrasonic;Heating and stirring uniform mixed solution until reaction is completed, to obtain palladium indium molybdenum nanometer tetrahedral catalyst;The palladium precursor, acetylacetone indium and hexacarbonyl molybdenum of the present application are directly dispersed in DMF, and uniform solution is obtained by ultrasonic, and the uniform solution after dispersion is stirred and heated, can directly obtain the palladium indium molybdenum nanometer tetrahedral catalyst with polyphase structure, the method only needs to mix all raw materials in one step to carry out reaction to obtain corresponding product, step simple, short cycle, high yield, good repeatability, reduce energy consumption and production cost, very suitable for industrialization large-scale production and application.

Description

Technical Field

[0001] This invention belongs to the field of nanocatalyst technology, and particularly relates to a multiphase tetrahedral palladium-indium-molybdenum nanocatalyst, its synthesis method, and its application. Background Technology

[0002] Fuel cells are a sustainable and clean energy source that can effectively convert chemical energy into electrical energy. In recent years, platinum-based catalysts have been recognized as one of the traditional high-efficiency catalysts. However, they have not been widely used commercially because platinum is a precious metal with high cost and very low reserves on Earth, making it difficult to use sustainably.

[0003] Palladium-based nanocatalysts possess advantages such as relatively low cost, relatively abundant reserves, and excellent catalytic performance. Furthermore, palladium and platinum share similar valence electron structures and lattice constants, making palladium a promising alternative to platinum. Therefore, the preparation and electrochemical performance study of palladium-based nanocatalysts is a highly valuable and important research topic.

[0004] Although palladium nanocatalysis is the preferred catalyst to replace platinum, palladium atoms often adsorb too strongly the intermediate product ions in the electrocatalytic oxidation of small organic molecule alcohols. This strong adsorption of intermediate products causes the active sites on the surface of palladium atoms to be gradually covered by the intermediate products during the catalytic reaction, thereby reducing the catalytic activity of palladium atoms.

[0005] Recent studies have shown that constructing a multiphase structure inside palladium catalysts is an effective solution to improve their catalytic efficiency. This is because there are many multiphase interfaces inside the catalyst, and these interface structures and different phase structures effectively improve the catalytic efficiency of palladium atoms in fuel cell catalytic reactions through synergistic effects.

[0006] However, current methods for synthesizing multiphase palladium-based nanocatalysts are complex, demanding, and involve numerous steps. For example, the synthesis process employs a series of complex experimental procedures, such as atmosphere protection and calcination. These complex procedures and demanding conditions greatly hinder the synthesis and application of such multiphase palladium-based nanocatalysts in actual production. Summary of the Invention

[0007] The purpose of this invention is to provide a multiphase tetrahedral palladium-indium-molybdenum nanocatalyst, its synthesis method, and its application, through a one-step synthesis of palladium-based nanocatalysts with multiphase structures.

[0008] This invention employs the following technical solution: a method for synthesizing multiphase tetrahedral palladium-in-molybdenum nanocatalysts, comprising the following steps:

[0009] Weigh out the palladium precursor, indium acetylacetone, and molybdenum hexacarbonyl;

[0010] Palladium precursor, indium acetylacetone, and molybdenum hexacarbonyl were dispersed in DMF and ultrasonicated to obtain a homogeneous mixed solution; wherein the concentration ratio of palladium precursor, indium acetylacetone, and molybdenum hexacarbonyl in the homogeneous mixed solution was 1.25:(0.88~4.00):2.5;

[0011] The mixed solution was heated and stirred until the reaction was complete to obtain a palladium indium molybdenum tetrahedral nanocatalyst; the heating temperature was 80–120 °C.

[0012] Among them, the palladium indium molybdenum nano-tetrahedral catalyst is a mixed structure of body-centered cubic palladium indium molybdenum and face-centered cubic palladium indium molybdenum.

[0013] Furthermore, the palladium precursor is palladium acetylacetone.

[0014] Furthermore, it includes the following steps:

[0015] 1) Disperse 10 mg palladium acetylacetone, 20 mg indium acetylacetone, and 20 mg molybdenum hexacarbonyl in 8 mL of DMF, sonicate for 10 min, and stir until completely dissolved to obtain a homogeneous mixed solution;

[0016] 2) Place the resulting homogeneous mixed solution in an oil bath at 80°C and react for 60 minutes;

[0017] After the reaction was complete and the mixture cooled naturally to room temperature, the reaction solution was transferred to a 15 mL centrifuge tube by centrifugation and washing. Then, 4 mL of ethanol was added, and the tube was centrifuged at 5000 rpm for 3 min. This centrifugation and washing cycle was repeated three times to obtain the multiphase palladium-indium-molybdenum tetrahedral nanocatalyst PdIn. 0.117 Mo 0.037 .

[0018] Furthermore, it includes the following steps:

[0019] 1) Disperse 10 mg palladium acetylacetone, 7 mg indium acetylacetone, and 20 mg molybdenum hexacarbonyl in 8 mL of DMF, sonicate for 10 min, and stir until completely dissolved to obtain the reaction solution;

[0020] 2) The obtained reaction solution was placed in an oil bath at 80°C and reacted for 60 minutes. After the reaction was completed, the solution was cooled to room temperature and then centrifuged and washed to obtain the multiphase palladium-indium-molybdenum tetrahedral nanocatalyst PdIn. 0.056 Mo 0.024 .

[0021] Furthermore, it includes the following steps:

[0022] 1) Disperse 10 mg palladium acetylacetone, 14 mg indium acetylacetone, and 20 mg molybdenum hexacarbonyl in 8 mL of DMF, sonicate for 10 min, and stir until completely dissolved to obtain the reaction solution;

[0023] 2) The obtained reaction solution was placed in an oil bath at 80°C and reacted for 60 minutes. After the reaction was completed, the solution was cooled to room temperature and then centrifuged and washed to obtain the multiphase palladium-indium-molybdenum tetrahedral nanocatalyst PdIn. 0.083 Mo 0.032 .

[0024] Furthermore, it includes the following steps:

[0025] 1) Disperse 10 mg palladium acetylacetone, 26 mg indium acetylacetone, and 20 mg molybdenum hexacarbonyl in 8 mL of DMF, sonicate for 10 min, and stir until completely dissolved to obtain the reaction solution;

[0026] 2) The obtained reaction solution was placed in an oil bath at 80°C and reacted for 60 minutes. After the reaction was completed, the solution was cooled to room temperature and then centrifuged and washed to obtain the multiphase palladium-indium-molybdenum tetrahedral nanocatalyst PdIn. 0.581 Mo 0.043 .

[0027] Furthermore, it includes the following steps:

[0028] 1) Disperse 10 mg palladium acetylacetone, 32 mg indium acetylacetone, and 20 mg molybdenum hexacarbonyl in 8 mL of DMF, sonicate for 10 min, and stir until completely dissolved to obtain the reaction solution;

[0029] 2) The obtained reaction solution was placed in an oil bath at 80°C and reacted for 60 minutes. After the reaction was completed, the solution was cooled to room temperature and then centrifuged and washed to obtain the multiphase palladium-indium-molybdenum tetrahedral nanocatalyst PdIn. 0.773 Mo 0.039 .

[0030] Another technical solution of the present invention: a multiphase tetrahedral palladium indium molybdenum nanocatalyst, prepared by the above method.

[0031] Another technical solution of the present invention: the application of the above-mentioned multiphase tetrahedral palladium indium molybdenum nanocatalyst, applying the multiphase tetrahedral palladium indium molybdenum nanocatalyst to the electrocatalytic reaction of ethanol and methanol oxidation.

[0032] The beneficial effects of this invention are as follows: This invention directly disperses palladium precursor, indium acetylacetonate, and molybdenum hexacarbonyl in DMF, obtains a homogeneous solution by ultrasonication, and then stirs and heats the dispersed homogeneous solution to directly obtain a multiphase structure palladium indium molybdenum tetrahedral nanocatalyst. This method only requires mixing all raw materials in one step to react and obtain the corresponding product. The steps are simple, the cycle is short, the yield is high, and the repeatability is good, which reduces energy consumption and production costs. It is very suitable for large-scale industrial production and application. Attached Figure Description

[0033] Figure 1 This is a bright-field transmission electron microscope image of the product in Example 1 of the present invention;

[0034] Figure 2 This is a dark-field transmission electron microscope image of the product in Example 1 of the present invention;

[0035] Figure 3 This is a high-resolution transmission electron microscope image of the product in Example 1 of the present invention;

[0036] Figure 4 This is a high-resolution transmission electron microscope image of the product in Example 1 of the present invention. Figure 3 (Enlarged portion of the rectangular region);

[0037] Figure 5 The X-ray diffraction pattern of the product in Example 1 of this invention;

[0038] Figure 6 This is a dimensional chart of the product in Embodiment 1 of the present invention;

[0039] Figure 7 This is a bright-field transmission electron microscope image of the product in Example 2 of the present invention;

[0040] Figure 8 This is a bright-field transmission electron microscope image of the product in Example 3 of the present invention;

[0041] Figure 9 This is a bright-field transmission electron microscope image of the product in Example 4 of the present invention;

[0042] Figure 10 This is a bright-field transmission electron microscope image of the product in Example 5 of the present invention;

[0043] Figure 11 This is a cyclic voltammetry curve of a multiphase palladium indium molybdenum nanotetrahedral catalyst in an application embodiment of the present invention;

[0044] Figure 12 This is a mass-normalized ethanol oxidation curve of the multiphase palladium indium molybdenum nanotetrahedral catalyst and commercial palladium on carbon in the application examples of this invention.

[0045] Figure 13 This is an area-normalized ethanol oxidation curve of the multiphase palladium indium molybdenum nanotetrahedral catalyst and commercial palladium on carbon in an application embodiment of the present invention.

[0046] Figure 14 The bar chart shows the mass activity of the multiphase palladium indium molybdenum nanotetrahedral catalyst and commercial palladium on carbon in the application examples of this invention (ethanol oxidation);

[0047] Figure 15 The above is a bar chart showing the area activity of the multiphase palladium indium molybdenum nanotetrahedral catalyst and commercial palladium on carbon in application examples of the present invention (ethanol oxidation).

[0048] Figure 16 This is a mass-normalized methanol oxidation curve of the multiphase palladium indium molybdenum nanotetrahedral catalyst and commercial palladium on carbon in the application examples of this invention.

[0049] Figure 17 This is an area-normalized methanol oxidation curve of the multiphase palladium indium molybdenum nanotetrahedral catalyst and commercial palladium on carbon in the application examples of the present invention.

[0050] Figure 18 The bar chart shows the mass activity of the multiphase palladium indium molybdenum nanotetrahedral catalyst and commercial palladium on carbon in the application examples of this invention (methanol oxidation);

[0051] Figure 19 This is a bar chart showing the area activity of the multiphase palladium indium molybdenum nanotetrahedral catalyst and commercial palladium on carbon in application examples of the present invention (methanol oxidation). Detailed Implementation

[0052] The present invention will now be described in detail with reference to the accompanying drawings and specific embodiments.

[0053] This invention discloses a method for synthesizing a multiphase tetrahedral palladium-in-molybdenum (PIM) nanocatalyst, comprising the following steps: weighing palladium precursor, indium acetylacetonate, and molybdenum hexacarbonyl; dispersing the palladium precursor, indium acetylacetonate, and molybdenum hexacarbonyl in DMF, and ultrasonicating to obtain a homogeneous mixed solution; wherein the concentration ratio of palladium precursor, indium acetylacetonate, and molybdenum hexacarbonyl in the homogeneous mixed solution is 1.25:(0.88~4.00):2.5; heating and stirring the mixed solution until the reaction is complete to obtain the palladium-in-molybdenum tetrahedral nanocatalyst; the heating temperature is 80~120℃; wherein the palladium-in-molybdenum tetrahedral nanocatalyst is a mixed structure of body-centered cubic palladium-in-molybdenum and face-centered cubic palladium-in-molybdenum. In this embodiment, the palladium-in-molybdenum tetrahedral nanocatalyst is PdIn x Mo y , where x takes values ​​from 0.056 to 0.773 and y takes values ​​from 0.024 to 0.043.

[0054] This invention directly disperses palladium precursor, indium acetylacetonate, and molybdenum hexacarbonyl in DMF, obtains a homogeneous solution by ultrasonication, and then stirs and heats the dispersed homogeneous solution to directly obtain a multiphase structured palladium indium molybdenum tetrahedral nanocatalyst. This method only requires mixing all raw materials in one step to react and obtain the corresponding product. The steps are simple, the cycle is short, the yield is high, and the repeatability is good, which reduces energy consumption and production costs, making it very suitable for large-scale industrial production and application.

[0055] In this invention, the solution of palladium precursor, indium acetylacetone, and molybdenum hexacarbonyl dispersed in DMF is pale yellow, and the product formed after heating is black. Therefore, the reaction is considered complete when the product is black. After the reaction is completed and naturally cooled to room temperature, the reaction product is centrifuged and washed to obtain palladium indium molybdenum tetrahedrons; wherein, the palladium indium molybdenum tetrahedrons have a multiphase structure.

[0056] In one specific implementation, the palladium precursor is palladium acetylacetonate, and molybdenum hexacarbonyl is used as a reducing agent.

[0057] Example 1:

[0058] 1) Disperse 10 mg palladium acetylacetone, 20 mg indium acetylacetone, and 20 mg molybdenum hexacarbonyl in 8 mL of DMF, sonicate for 10 min, and stir until completely dissolved to obtain a homogeneous mixed solution;

[0059] 2) Place the resulting homogeneous mixed solution in an oil bath at 80°C and react for 60 minutes;

[0060] After the reaction was complete and the mixture cooled naturally to room temperature, the reaction solution was transferred to a 15 mL centrifuge tube by centrifugation and washing. Then, 4 mL of ethanol was added, and the tube was centrifuged at 5000 rpm for 3 min. This cycle of centrifugation and washing was repeated three times to obtain the multiphase structure PdIn. 0.117 Mo 0.037 Nano-tetrahedral catalyst.

[0061] like Figure 1 and Figure 2 The images show the bright-field and dark-field transmission electron microscopy characterization of the tetrahedral palladium indium molybdenum nanocatalyst with a multiphase structure. Both images clearly show that the palladium indium molybdenum nanocatalyst has a distinct and uniform tetrahedral structure.

[0062] like Figure 3 The image shown is a high-resolution transmission electron microscope image of a single tetrahedron, which clearly shows the high crystallinity of the product. Figure 4 yes Figure 3 A magnified image of the rectangular region clearly shows the synthesized PdIn. 0.117 Mo 0.037Nanocatalysts have two phase structures: ordered intermetallic structures and disordered face-centered cubic structures.

[0063] like Figure 5 The figure shown is a size statistics chart of the product of this embodiment. It can be seen from the figure that the size of a single nanotetrahedron is approximately 23.9 nm.

[0064] like Figure 6 The image shows the X-ray diffraction pattern of the product, further demonstrating that this palladium-indium-molybdenum nano-tetrahedral catalyst possesses a multiphase structure. The four typical diffraction peaks at 40.03°, 46.57°, 68.04°, and 82.01° correspond to PdIn, respectively. 0.117 Mo 0.037 The (111), (200), (220), and (311) crystal planes belong to a typical face-centered cubic crystal structure, and 30.57°, 51.07°, and 60.67° correspond to PdIn 0.117 Mo 0.037 The (011), (112), and (022) crystal planes belong to the body-centered cubic structure. This further proves that the palladium indium molybdenum nanotetrahedral catalyst is a hybrid structure of face-centered cubic and body-centered cubic.

[0065] Example 2:

[0066] 1) Disperse 10 mg palladium acetylacetone, 7 mg indium acetylacetone, and 20 mg molybdenum hexacarbonyl in 8 mL of DMF, sonicate for 10 min, and stir until completely dissolved to obtain the reaction solution;

[0067] 2) The obtained reaction solution was placed in an oil bath at 80°C and reacted for 60 minutes. After the reaction was completed, the solution was cooled to room temperature and then centrifuged and washed to obtain PdIn with a multiphase structure. 0.056 Mo 0.024 Nano-tetrahedral catalyst.

[0068] like Figure 7 The image shown is a bright-field transmission electron microscope (TEM) image of the product of this embodiment. It can be seen from the image that the product has a good tetrahedral structure.

[0069] Example 3:

[0070] 1) Disperse 10 mg palladium acetylacetone, 14 mg indium acetylacetone, and 20 mg molybdenum hexacarbonyl in 8 mL of DMF, sonicate for 10 min, and stir until completely dissolved to obtain the reaction solution;

[0071] 2) The obtained reaction solution was placed in an oil bath at 80°C and reacted for 60 minutes. After the reaction was completed, the solution was cooled to room temperature and then centrifuged and washed to obtain PdIn with a multiphase structure. 0.083 Mo 0.032Nano-tetrahedral catalyst.

[0072] like Figure 8 The image shown is a bright-field transmission electron microscope (TEM) image of the product of this embodiment. It can be seen from the image that the product has a good tetrahedral structure.

[0073] Example 4:

[0074] 1) Disperse 10 mg palladium acetylacetone, 26 mg indium acetylacetone, and 20 mg molybdenum hexacarbonyl in 8 mL of DMF, sonicate for 10 min, and stir until completely dissolved to obtain the reaction solution;

[0075] 2) The obtained reaction solution was placed in an oil bath at 80°C and reacted for 60 minutes. After the reaction was completed, the solution was cooled to room temperature and then centrifuged and washed to obtain PdIn with a multiphase structure. 0.581 Mo 0.043 Nano-tetrahedral catalyst.

[0076] like Figure 9 The image shown is a bright-field transmission electron microscope (TEM) image of the product of this embodiment. It can be seen from the image that the product has a good tetrahedral structure.

[0077] Example 5:

[0078] 1) Disperse 10 mg palladium acetylacetone, 32 mg indium acetylacetone, and 20 mg molybdenum hexacarbonyl in 8 mL of DMF, sonicate for 10 min, and stir until completely dissolved to obtain the reaction solution;

[0079] 2) The obtained reaction solution was placed in an oil bath at 80°C and reacted for 60 minutes. After the reaction was completed, the solution was cooled to room temperature and then centrifuged and washed to obtain PdIn with a multiphase structure. 0.773 Mo 0.039 Nano-tetrahedral catalyst.

[0080] like Figure 10 The image shown is a bright-field transmission electron microscope (TEM) image of the product of this embodiment. It can be seen from the image that the product has a good tetrahedral structure.

[0081] Example 6:

[0082] 1) Disperse 10 mg palladium acetylacetone, 20 mg indium acetylacetone, and 20 mg molybdenum hexacarbonyl in 8 mL of DMF, sonicate for 10 min, and stir until completely dissolved to obtain the reaction solution;

[0083] 2) The obtained reaction solution was placed in an oil bath at 90°C and reacted for 60 minutes. After the reaction was completed, the solution was cooled to room temperature and then centrifuged and washed to obtain a palladium indium molybdenum nanotetrahedral catalyst with a multiphase structure.

[0084] Example 7:

[0085] 1) Disperse 10 mg palladium acetylacetone, 20 mg indium acetylacetone, and 20 mg molybdenum hexacarbonyl in 8 mL of DMF, sonicate for 10 min, and stir until completely dissolved to obtain the reaction solution;

[0086] 2) The obtained reaction solution was placed in an oil bath at 100°C and reacted for 60 minutes. After the reaction was completed, the solution was cooled to room temperature and then centrifuged and washed to obtain a palladium indium molybdenum nanotetrahedral catalyst with a multiphase structure.

[0087] Example 8:

[0088] 1) Disperse 10 mg palladium acetylacetone, 20 mg indium acetylacetone, and 20 mg molybdenum hexacarbonyl in 8 mL of DMF, sonicate for 10 min, and stir until completely dissolved to obtain the reaction solution;

[0089] 2) The obtained reaction solution was placed in an oil bath at 110°C and reacted for 60 minutes. After the reaction was completed, the solution was cooled to room temperature and then centrifuged and washed to obtain a palladium indium molybdenum nanotetrahedral catalyst with a multiphase structure.

[0090] Example 9:

[0091] 1) Disperse 10 mg palladium acetylacetone, 20 mg indium acetylacetone, and 20 mg molybdenum hexacarbonyl in 8 mL of DMF, sonicate for 10 min, and stir until completely dissolved to obtain the reaction solution;

[0092] 2) The obtained reaction solution was placed in an oil bath at 120°C and reacted for 60 minutes. After the reaction was completed, the solution was cooled to room temperature and then centrifuged and washed to obtain a palladium indium molybdenum nanotetrahedral catalyst with a multiphase structure.

[0093] The present invention also discloses a multiphase tetrahedral palladium-in-molybdenum nanocatalyst, which is prepared by the above method and has a multiphase structure with ordered intermetallic structure and disordered face-centered cubic structure.

[0094] This invention discloses the application of a multiphase tetrahedral palladium indium molybdenum nanocatalyst, which is used in the electrocatalytic reaction of ethanol and methanol oxidation.

[0095] Specifically, when this multiphase palladium-indium-molybdenum nanotetrahedron is used in the electrocatalytic reaction of ethanol oxidation:

[0096] The catalyst (1.2 mg) was dispersed in 1 mL of a mixed solution of water and ethanol (water:ethanol = 1:1); then 20 μL of Nafion solution was added to the above mixed solution and the mixture was sonicated for 20 min; 6 μL of the sonicated solution was then dropped onto a surface with an area of ​​0.196 cm². 2 Electrochemical tests were performed on the glassy carbon electrode surface after the sample had dried.

[0097] The electrochemical test was conducted at room temperature, with a Hg / HgO electrode as the reference electrode and a platinum mesh electrode (1×1 cm) as the auxiliary electrode. 2 A three-electrode system was used in a 1M KOH medium, such as... Figure 11 As shown, the cyclic voltammetry curves were tested under a N2 atmosphere at a scan rate of 50 mV / s and a scan range of 0.05 V to 1.2 V. Figure 12 , 13 As shown, the scans were performed in a mixed solution of 1M KOH and 1M C2H5OH at a scan rate of 50 mV / s.

[0098] Transform the test data, such as Figure 14 and Figure 15 As shown, these are the activity values ​​per unit mass of palladium (…). Figure 14 ) and the activity of palladium per unit area ( Figure 15 It can be clearly observed that, compared with commercially available Pd / C nanocatalysts, the catalytic activity of the heterogeneous palladium-indium-molybdenum nanotetrahedra prepared in this invention is significantly enhanced for the ethanol oxidation reaction. Among them, PdIn... 0.117 Mo 0.037 The nanocatalyst possesses the best mass activity (2668.49 mA mg). Pd -1 ) and surface activity (8.11 mAcm) -2 ), is a commercial Pd / C nanocatalyst (655.83 mA mg). Pd -1 2.58mA cm -2 ) is 4.06 and 3.14 times that of ).

[0099] In another embodiment, when the multiphase palladium-indium-molybdenum nanotetrahedron is used as a catalyst in the methanol oxidation electrocatalytic reaction:

[0100] The catalyst (1.2 mg) was dispersed in 1 mL of a mixed solution of water and ethanol (water:ethanol = 1:1); then 20 μL of Nafion solution was added to the above mixed solution and the mixture was sonicated for 20 min; 6 μL of the sonicated solution was then dropped onto a surface with an area of ​​0.196 cm². 2 Electrochemical tests were performed on the glassy carbon electrode surface after the sample was dried.

[0101] The electrochemical test was conducted at room temperature, with a Hg / HgO electrode as the reference electrode and a platinum mesh electrode (1×1 cm) as the auxiliary electrode. 2 A three-electrode system was used in a 1M KOH medium, such as... Figure 11 As shown, the cyclic voltammetry curves were tested under a N2 atmosphere at a scan rate of 50 mV / s and a scan range of 0.05 V to 1.2 V. Figure 16 , 17 As shown, the scan was performed in a mixed solution of 1M KOH and 1M CH3OH at a scan rate of 50 mV / s.

[0102] Transform the test data, such as Figure 18 and Figure 19 As shown, these are the activity values ​​per unit mass of palladium (…). Figure 18 ) and the activity of palladium per unit area ( Figure 19 It can be clearly observed that, compared with commercially available Pd / C nanocatalysts, the catalytic activity of the heterogeneous palladium-indium-molybdenum nanotetrahedra prepared in this invention is significantly enhanced for the methanol oxidation reaction. Among them, PdIn... 0.117 Mo 0.037 The nanocatalyst possesses the best mass activity (2205.6 mA mg). Pd -1 ) and area activity (6.67 mA cm) -2 ), is a commercial Pd / C nanocatalyst (458.5 mA mg). Pd -1 1.96mA cm -2 ) 4.81 and 3.40 times.

Claims

1. A method for synthesizing multiphase tetrahedral palladium-indium-molybdenum nanocatalysts, characterized in that, Includes the following steps: Weigh out the palladium precursor, indium acetylacetone, and molybdenum hexacarbonyl; The palladium precursor, indium acetylacetone, and molybdenum hexacarbonyl were dispersed in DMF and ultrasonicated to obtain a homogeneous mixed solution; wherein the mass concentration ratio of the palladium precursor, indium acetylacetone, and molybdenum hexacarbonyl in the homogeneous mixed solution was 1.25 : (0.88~4.00) : 2.5; The homogeneous mixed solution was heated and stirred until the reaction was complete to obtain a palladium indium molybdenum tetrahedral nanocatalyst; the heating temperature was 80~120℃. The palladium indium molybdenum nano-tetrahedral catalyst is a mixture of body-centered cubic palladium indium molybdenum and face-centered cubic palladium indium molybdenum.

2. The method for synthesizing the multiphase tetrahedral palladium-indium-molybdenum nanocatalyst as described in claim 1, characterized in that, The palladium precursor is palladium acetylacetonate.

3. The method for synthesizing the multiphase tetrahedral palladium-indium-molybdenum nanocatalyst as described in claim 2, characterized in that, Includes the following steps: 1) Disperse 10 mg palladium acetylacetone, 20 mg indium acetylacetone, and 20 mg molybdenum hexacarbonyl in 8 mL of DMF, sonicate for 10 min, and stir until completely dissolved to obtain a homogeneous mixed solution; 2) Place the resulting homogeneous mixed solution in an oil bath at 80°C and react for 60 minutes; After the reaction was complete and the mixture cooled naturally to room temperature, the reaction solution was transferred to a 15 mL centrifuge tube by centrifugation and washing. Then, 4 mL of ethanol was added, and the tube was centrifuged at 5000 rpm for 3 min. This centrifugation and washing cycle was repeated three times to obtain the multiphase palladium-indium-molybdenum tetrahedral nanocatalyst PdIn. 0.117 Mo 0.037 .

4. The method for synthesizing the multiphase tetrahedral palladium-indium-molybdenum nanocatalyst as described in claim 2, characterized in that, Includes the following steps: 1) Disperse 10 mg palladium acetylacetone, 7 mg indium acetylacetone, and 20 mg molybdenum hexacarbonyl in 8 mL of DMF, sonicate for 10 min, and stir until completely dissolved to obtain the reaction solution; 2) The obtained reaction solution was placed in an oil bath at 80°C and reacted for 60 minutes. After the reaction was completed, the solution was cooled to room temperature and then centrifuged and washed to obtain the multiphase palladium-indium-molybdenum tetrahedral nanocatalyst PdIn. 0.056 Mo 0.024 .

5. The method for synthesizing the multiphase tetrahedral palladium-indium-molybdenum nanocatalyst as described in claim 2, characterized in that, Includes the following steps: 1) Disperse 10 mg palladium acetylacetonate, 14 mg indium acetylacetonate, and 20 mg molybdenum hexacarbonyl in 8 mL of DMF, sonicate for 10 min, and stir until completely dissolved to obtain the reaction solution; 2) The obtained reaction solution was placed in an oil bath at 80°C and reacted for 60 minutes. After the reaction was completed, the solution was cooled to room temperature and then centrifuged and washed to obtain the multiphase palladium-indium-molybdenum tetrahedral nanocatalyst PdIn. 0.083 Mo 0.032 .

6. The method for synthesizing the multiphase tetrahedral palladium-indium-molybdenum nanocatalyst as described in claim 2, characterized in that, Includes the following steps: 1) Disperse 10 mg palladium acetylacetone, 26 mg indium acetylacetone, and 20 mg molybdenum hexacarbonyl in 8 mL of DMF, sonicate for 10 min, and stir until completely dissolved to obtain the reaction solution; 2) The obtained reaction solution was placed in an oil bath at 80°C and reacted for 60 minutes. After the reaction was completed, the solution was cooled to room temperature and then centrifuged and washed to obtain the multiphase palladium-indium-molybdenum tetrahedral nanocatalyst PdIn. 0.581 Mo 0.043 .

7. The method for synthesizing the multiphase tetrahedral palladium-indium-molybdenum nanocatalyst as described in claim 2, characterized in that, Includes the following steps: 1) Disperse 10 mg palladium acetylacetone, 32 mg indium acetylacetone, and 20 mg molybdenum hexacarbonyl in 8 mL of DMF, sonicate for 10 min, and stir until completely dissolved to obtain the reaction solution; 2) The obtained reaction solution was placed in an oil bath at 80°C and reacted for 60 minutes. After the reaction was completed, the solution was cooled to room temperature and then centrifuged and washed to obtain the multiphase palladium-indium-molybdenum tetrahedral nanocatalyst PdIn. 0.773 Mo 0.039 .

8. A multiphase tetrahedral palladium-indium-molybdenum nanocatalyst, characterized in that, It is prepared by the method described in any one of claims 1-7.

9. The application of the multiphase tetrahedral palladium-indium-molybdenum nanocatalyst as described in claim 8, characterized in that, The multiphase tetrahedral palladium-indium-molybdenum nanocatalyst was applied to the electrocatalytic reaction of ethanol or methanol oxidation.

Images