Ternary metal palladium-based nanoparticle material, preparation method and application thereof
The preparation of ternary palladium-based nanoparticles by a one-step reduction method solves the problem of poor hydrogen sensing performance of multi-element palladium-based nanoparticles, achieving rapid response and stability, simplifying the preparation process, and making it suitable for safe detection of hydrogen gas.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- CHINA PETROLEUM & CHEMICAL CORP
- Filing Date
- 2024-11-27
- Publication Date
- 2026-05-29
AI Technical Summary
Existing multi-metal palladium-based nanoparticles have poor hydrogen sensing performance, and their preparation methods are cumbersome and the nanoparticles are large in size. Current technologies cannot meet the requirements for rapid response and stability.
A one-step reduction method was used to synthesize ternary palladium-based nanoparticles containing palladium, copper, and a third transition metal. Alloy nanoparticles with a particle size of 10-100 nm were prepared by mixing palladium precursor, copper precursor, third metal precursor, morphology control agent, and reducing agent in a solvent.
It achieves rapid response to hydrogen leakage at room temperature, possesses strong mechanical strength and chemical stability, simplifies the preparation process, reduces costs, and facilitates large-scale production.
Smart Images
Figure CN122105166A_ABST
Abstract
Description
Technical Field
[0001] This invention relates to the field of hydrogen sensing material preparation technology, specifically to a ternary palladium-based nanoparticle material, its preparation method, and its application. Background Technology
[0002] At room temperature (RT), palladium (Pd) can reversibly react with H2, catalytically dissociating hydrogen into hydrogen atoms to form palladium hydride (PdHx), which has a higher resistivity than Pd. Quantitative detection of H2 can be achieved by detecting the resistance signal from a Pd-based sensor. However, single palladium metal often exhibits poor hydrogen sensing response and slow reaction kinetics, and even hydrogen sensors based on nanoscale Pd-based hydrogen-sensitive materials still suffer from insufficient response and recovery speeds. Compared to single metals, multi-metal nanoparticles exhibit superior sensing performance due to synergistic effects between metals. Therefore, researchers have begun to focus on the preparation of multi-metal palladium-based nanoparticles. However, the hydrogen sensing performance of existing multi-metal palladium-based nanoparticles still needs improvement.
[0003] The main methods for preparing palladium-based nanoparticles include electrodeposition, template method, and chemical reduction method. Electrodeposition suffers from poor reproducibility and impure product composition, while the template method requires pre-preparation or post-removal template processes, making it cumbersome. In contrast, the chemical reduction method is simple to operate, has good reproducibility, and can yield products with uniform morphology and size. Currently, the seed method, a two-step method, is commonly used to prepare palladium-based nanoparticles. This method not only requires the pre-preparation of palladium-based nanoparticles with a specific morphology as seed crystals, but also necessitates the addition of morphology control agents in subsequent reactions to guide or restrict the growth of specific crystal faces. This allows for the continued growth of palladium-based nanoparticles with different crystal faces based on the original morphology. This method is cumbersome and results in relatively large sizes of multi-metal nanoparticles.
[0004] Therefore, there is an urgent need to provide a new type of Pd-based bimetallic hydrogen-sensitive material with diverse morphologies and a simple preparation method. Summary of the Invention
[0005] The purpose of this invention is to overcome the problems of poor hydrogen sensing performance of existing palladium-based multi-metal palladium nanoparticles and the cumbersome two-step preparation method and large nanoparticle size of palladium-based bimetallic nanomaterials. This invention provides ternary palladium-based nanoparticle materials, their preparation method, and applications. These ternary palladium-based nanoparticle materials contain palladium, copper, and a third specific metal, which exist in an alloy form. Ternary palladium-based nanoparticle materials with this characteristic exhibit fast hydrogen response time at room temperature and strong mechanical strength and chemical stability.
[0006] To achieve the above objectives, the present invention provides a ternary palladium-based nanoparticle material containing palladium, copper, and a third metal, wherein the palladium, copper, and the third metal exist in an alloy form, and the third metal is at least one of the metal elements in Group IIB and / or Group VIII other than palladium.
[0007] Preferably, the molar ratio of palladium, copper and the third metal is 1-10:1-10:1.
[0008] Preferably, the particle size of the ternary palladium-based nanoparticle material is 10-100 nm.
[0009] Preferably, the third metal is selected from nickel, cobalt, zinc or iron.
[0010] The second aspect of the present invention provides a method for preparing ternary palladium-based nanoparticle materials, the method comprising: reacting a palladium precursor, a copper precursor, a third metal precursor, a morphology control agent, a reducing agent and a surfactant in the presence of a solvent;
[0011] The third metal in the third metal precursor is at least one metal element from Group IIB and / or Group VIII, excluding palladium.
[0012] Preferably, the molar ratio of palladium precursor: copper precursor: third metal precursor: morphology control agent: reducing agent is 1:0.1-1:0.1-1:0.5-1:5-20.
[0013] Preferably, the palladium precursor is selected from one or more of palladium acetylacetonate, palladium chloride, and palladium nitrate.
[0014] Preferably, the copper precursor is selected from one or more of copper acetylacetonate, copper sulfate, and copper nitrate.
[0015] Preferably, the third metal precursor is selected from nickel acetylacetonate, cobalt acetylacetonate, zinc acetylacetonate, or iron acetylacetonate.
[0016] Preferably, the morphology control agent is a halide.
[0017] Preferably, the morphology control agent is selected from one or more of ferric chloride, ferric bromide, potassium fluoride, potassium chloride, potassium bromide, potassium iodide, sodium fluoride, sodium chloride, sodium bromide, and sodium iodide.
[0018] Preferably, the reducing agent is selected from one or more of ascorbic acid, sodium borohydride, and sodium hypophosphite.
[0019] Preferably, the surfactant is selected from one or more of CTAB, CTAC, PVP, CPC, SDBS and oleylamine.
[0020] Preferably, the reaction conditions include: a temperature of 100-200℃ and a time of 5-20h.
[0021] A third aspect of the present invention provides a ternary palladium-based nanoparticle material prepared by the method described above.
[0022] The fourth aspect of the present invention provides a ternary palladium-based nanoparticle material as described above, or the application of the ternary palladium-based nanoparticle material as described above as a hydrogen-sensitive material.
[0023] The fifth aspect of the present invention provides a method for testing the performance of hydrogen sensing, the method comprising: placing a hydrogen-sensitive material in a sealed device, introducing a mixed gas containing hydrogen and a protective gas to react, and testing the resistance at different reaction times; wherein the hydrogen-sensitive material contains the ternary palladium-based nanoparticle material described above.
[0024] Preferably, the hydrogen content in the mixed gas is 0.02-2% by volume.
[0025] Preferably, the reaction conditions include: a temperature of 15-30°C and a time of 100-3000 s.
[0026] Compared with the prior art, the present invention has at least the following advantages:
[0027] (1) The ternary palladium-based nanoparticle material provided by the present invention contains three specific metal elements, and the three metals exist in the form of an alloy. The ternary palladium-based nanoparticle material with this feature has a fast response time to hydrogen, strong mechanical strength and chemical stability, and can quickly detect and respond to hydrogen leakage in the environment at room temperature, thereby ensuring its safe use.
[0028] (2) The method described in this invention employs a liquid-phase reduction method (one-step reduction method), which directly mixes and heats a surfactant, reducing agent, morphology control agent, and metal precursor to prepare ternary palladium-based nanoparticle materials. This method is simple, environmentally friendly, uses inexpensive raw materials, and is easy to mass-produce and apply. Attached Figure Description
[0029] Figure 1 These are TEM images of the materials prepared in Example 1;
[0030] Figures 2-4 The figures show the resistance curves of the materials prepared in Example 1, Comparative Example 1, and Comparative Example 2 over time. Detailed Implementation
[0031] The specific embodiments of the present invention will be described in detail below with reference to the accompanying drawings. It should be understood that the specific embodiments described herein are for illustration and explanation only and are not intended to limit the present invention.
[0032] The endpoints and any values of the ranges disclosed herein are not limited to the precise ranges or values, and these ranges or values should be understood to include values close to these ranges or values. For numerical ranges, the endpoint values of the various ranges, the endpoint values of the various ranges and individual point values, and individual point values can be combined with each other to obtain one or more new numerical ranges, which should be considered as specifically disclosed herein.
[0033] The first aspect of the present invention provides a ternary palladium-based nanoparticle material containing palladium, copper and a third metal, wherein the palladium, copper and the third metal exist in an alloy form, wherein the third metal is at least one of the metal elements in Group IIB and / or Group VIII other than palladium, that is, the third metal is a metal element in Group IIB and / or Group VIII, but cannot be palladium.
[0034] Through research, the inventors of this invention discovered that ternary palladium-based nanoparticles containing the three different metals described in this invention have a fast response time to hydrogen, strong mechanical strength, and chemical stability. They can quickly detect and respond to hydrogen leaks in the environment at room temperature, thereby ensuring their safe use.
[0035] In this invention, the third metal cannot be copper. In specific embodiments, the third metal can be any transition metal other than copper that is conventionally used in the art.
[0036] To improve the hydrogen sensing performance of the ternary palladium-based nanoparticle material, in a preferred embodiment, the third metal is selected from nickel, cobalt, zinc, or iron. To further improve the hydrogen sensing performance of the ternary palladium-based nanoparticle material, the third metal is nickel.
[0037] In this invention, in order to improve the hydrogen sensing performance of the ternary palladium-based nanoparticle material, in a preferred embodiment, the molar ratio of palladium, copper and the third metal is 1-10:1-10:1.
[0038] In this invention, the nanoparticles of the ternary palladium-based nanoparticle material are relatively small in size.
[0039] In a specific embodiment, the particle size of the ternary palladium-based nanoparticle material can be 10-100 nm.
[0040] A second aspect of the present invention provides a method for preparing ternary palladium-based nanoparticle materials, the method comprising: reacting a palladium precursor, a copper precursor, a third metal precursor, a morphology control agent, a reducing agent and a surfactant in the presence of a solvent; wherein the third metal in the third metal precursor is at least one metal element other than palladium from Group IIB and / or Group VIII.
[0041] The preparation method provided by this invention is simple and easy to operate. The target product can be obtained by mixing palladium precursor, copper precursor, third metal precursor, morphology control agent, reducing agent and surfactant in one step.
[0042] In order to obtain a ternary palladium-based nanoparticle material with a suitable ratio of palladium, copper and third metal and excellent hydrogen sensing performance, in a specific embodiment, the molar ratio of palladium precursor: copper precursor: third metal precursor: morphology control agent: reducing agent can be 1:0.1-1:0.1-1:0.5-1:5-20.
[0043] In this invention, the palladium precursor can be any palladium salt well known to those skilled in the art. In a specific embodiment, the palladium precursor can be selected from one or more of palladium acetylacetonate, palladium chloride, and palladium nitrate. In a specific embodiment, the palladium precursor is palladium acetylacetonate.
[0044] In this invention, the copper precursor can be any palladium salt well known to those skilled in the art. In specific embodiments, the copper precursor can be selected from one or more of copper acetylacetonate, copper sulfate, and copper nitrate.
[0045] In a preferred embodiment, in order to improve the hydrogen sensing performance of the prepared ternary palladium-based nanoparticle material, the third metal precursor may be selected from nickel acetylacetonate, cobalt acetylacetonate, zinc acetylacetonate, or iron acetylacetonate.
[0046] In a more preferred embodiment, the third metal precursor is nickel acetylacetonate.
[0047] In this invention, the morphology control agent can be any of the various halides conventionally used in the art.
[0048] In specific embodiments, the morphology control agent may be selected from one or more of ferric chloride, ferric bromide, potassium fluoride, potassium chloride, potassium bromide, potassium iodide, sodium fluoride, sodium chloride, sodium bromide, and sodium iodide. In this invention, the various halides listed include crystalline hydrates.
[0049] In a preferred embodiment, the morphology control agent is ferric chloride and / or ferric chloride hexahydrate.
[0050] In this invention, the reducing agent can be a conventional choice in the art, as long as it can reduce the metal elements in the palladium precursor, copper precursor, and third metal precursor to elemental form, and finally obtain a ternary alloy.
[0051] In a specific embodiment, the reducing agent may be selected from one or more of ascorbic acid, sodium borohydride, and sodium hypophosphite.
[0052] In a preferred embodiment, the reducing agent is ascorbic acid.
[0053] In this invention, the surfactant can be a conventional choice in the art. In a specific embodiment, the surfactant is selected from one or more of CTAB (hexadecyltrimethylammonium bromide), CTAC (hexadecyltrimethylammonium chloride), PVP (polyvinylpyrrolidone), CPC (hexadecylpyridine chloride), SDBS (hexadecylpyridine chloride), and oleylamine.
[0054] In this invention, some surfactants are liquid and some are solid. Liquid surfactants can dissolve other raw materials on their own, in which case no additional solvent is needed; however, when solid surfactants are used, additional solvent needs to be added in order to dissolve other raw materials.
[0055] In a specific embodiment, when the surfactant is oleylamine, since oleylamine is liquid, it can act as a solvent to dissolve the palladium precursor, copper precursor, third metal precursor, morphology control agent, and reducing agent. In this embodiment, the method for preparing ternary palladium-based nanoparticle materials includes reacting the palladium precursor, copper precursor, third metal precursor, morphology control agent, reducing agent, and surfactant.
[0056] In a specific embodiment, when the surfactant is CTAB, CTAC, PVP, CPC, or SDBS, CTAB, CTAC, PVP, CPC, and SDBS are in solid form. In this embodiment, water can be added as a solvent to dissolve the palladium precursor, copper precursor, third metal precursor, morphology control agent, and reducing agent. In this embodiment, the method for preparing ternary palladium-based nanoparticle materials includes reacting the palladium precursor, copper precursor, third metal precursor, morphology control agent, reducing agent, surfactant, and water.
[0057] In this invention, there is no particular limitation on the amount of surfactant used; it can be added according to conventional standards.
[0058] In this invention, after mixing palladium precursor, copper precursor, third metal precursor, morphology control agent, reducing agent and surfactant, the mixture can be ultrasonically treated for 0.5-1.5 hours before the reaction to ensure that the raw materials are fully dissolved and mixed evenly.
[0059] In this invention, after the reaction is complete, a gel-like product can be collected by centrifugation, then washed multiple times with a mixture of acetone, ethanol and cyclohexane, and dried under vacuum to obtain ternary palladium-based nanoparticle materials.
[0060] In a specific embodiment, the reaction temperature can be 100-200℃, for example 100℃, 120℃, 140℃, 150℃, 160℃, 180℃ or 200℃; the time can be 5-20h, for example 5h, 8h, 10h, 12h, 15h, 16h, 18h or 20h.
[0061] A third aspect of the present invention provides a ternary palladium-based nanoparticle material prepared by the method described above.
[0062] In a preferred embodiment, the ternary palladium-based nanoparticle material contains palladium, copper, and a third metal, and the palladium, copper, and third metal exist in an alloy form, wherein the third metal is a transition metal other than copper.
[0063] In a preferred embodiment, the molar ratio of palladium, copper and the third metal is 1-10:1-10:1.
[0064] In a preferred embodiment, the particle size of the ternary palladium-based nanoparticle material is 10-100 nm.
[0065] In a preferred embodiment, the third metal is selected from nickel, cobalt, zinc, or iron.
[0066] The fourth aspect of this invention provides an application of the aforementioned ternary palladium-based nanoparticle material as a hydrogen-sensitive material.
[0067] The ternary palladium-based nanoparticle material described in this invention, as a novel hydrogen-sensitive material, has advantages over other hydrogen-sensitive materials such as metal oxides, including no need for heating, low power consumption, good stability, and fast response speed.
[0068] The fifth aspect of the present invention provides a method for testing the performance of hydrogen sensing, the method comprising: placing a hydrogen-sensitive material in a sealed device, introducing a mixed gas containing hydrogen and a protective gas to react, and testing the resistance at different reaction times; wherein the hydrogen-sensitive material contains the ternary palladium-based nanoparticle material described above.
[0069] In a specific embodiment, ternary palladium-based nanoparticles are mixed with terpineol and coated onto a hexagonal sensor base. After drying and aging, a molded hydrogen-sensitive composite material is obtained. The molded hydrogen-sensitive composite material is then placed in a sealed device for hydrogen sensing performance testing.
[0070] In the method for testing the hydrogen sensing performance of the present invention, the type of sealing device is not limited, as long as it is a sealed device that can allow gas to pass through, such as a sealed chamber.
[0071] In a specific embodiment, the hydrogen content in the mixed gas can be 0.02-2% by volume, for example, 0.02% by volume, 0.05% by volume, 0.08% by volume, 0.1% by volume, 0.2% by volume, 0.3% by volume, 0.4% by volume, 0.5% by volume, 0.6% by volume, 0.7% by volume, 0.8% by volume, 0.9% by volume, 1% by volume, 1.2% by volume, 1.4% by volume, 1.5% by volume, 1.6% by volume, 1.8% by volume, or 2% by volume.
[0072] In this invention, the protective gas can be a conventional choice in the art; specifically, the protective gas can be nitrogen and / or air.
[0073] In a specific embodiment, the reaction conditions include: a temperature of 15-30°C (room temperature); and a time of 100-3000 seconds.
[0074] In this invention, the instrument used for hydrogen sensing performance testing is the CGS-8 intelligent gas-sensitive analysis system from Elitet Technology Co., Ltd.
[0075] The hydrogen-sensitive material (hydrogen sensing material) provided by this invention directly addresses the leakage monitoring and safety issues of hydrogen, a new generation of clean energy. It can quickly detect and respond to hydrogen leaks in the environment at room temperature, thereby ensuring its safe use. It can be used in hydrogen production, hydrogen refueling, hydrogen storage and other hydrogen usage processes.
[0076] The present invention will be described in detail below through examples, but the scope of protection of the present invention is not limited thereto. Unless otherwise specified, all reagents used in the following examples and comparative examples are commercially available products.
[0077] The following examples illustrate the preparation process of ternary palladium-based nanoparticle materials.
[0078] Example 1
[0079] (1) Dissolve 8 mg palladium acetylacetonate, 6.9 mg copper acetylacetonate, 6.8 mg nickel acetylacetonate, 5.4 mg ferric chloride hexahydrate and 35.6 mg ascorbic acid in 5 mL of oleylamine and sonicate for 60 min. The molar ratio of palladium acetylacetonate, copper acetylacetonate, nickel acetylacetonate, ferric chloride hexahydrate and ascorbic acid is 1:1:1:0.77:7.7.
[0080] (2) The mixture obtained in step (1) was heated in an oil bath at 200°C for 12 hours. The gel-like product was collected by centrifugation and then washed three times with a mixture of acetone, ethanol and cyclohexane. The product was dried under vacuum at 60°C for 24 hours.
[0081] TEM image of the product prepared in Example 1 is shown below. Figure 1 As shown, from Figure 1 It can be seen that it is mainly composed of spherical nanoparticles.
[0082] Example 2
[0083] The method was implemented according to Example 1, except that 6.8 mg of nickel acetylacetone was replaced with 9.35 mg of iron acetylacetone, wherein the molar ratio of palladium acetylacetone, copper acetylacetone, iron acetylacetone, ferric chloride hexahydrate and ascorbic acid was 1:1:1:0.77:7.7.
[0084] Example 3
[0085] The method was implemented according to Example 1, except that 6.8 mg of nickel acetylacetone was replaced with 6.83 mg of cobalt acetylacetone, wherein the molar ratio of palladium acetylacetone, copper acetylacetone, cobalt acetylacetone, ferric chloride hexahydrate and ascorbic acid was 1:1:1:0.77:7.7.
[0086] Example 4
[0087] The method was implemented according to Example 1, except that 6.8 mg of nickel acetylacetone was replaced with 6.95 mg of zinc acetylacetone, wherein the molar ratio of palladium acetylacetone, copper acetylacetone, zinc acetylacetone, ferric chloride hexahydrate and ascorbic acid was 1:1:1:0.77:7.7.
[0088] Example 5
[0089] The method was implemented according to Example 1, except that 8 mg of palladium acetylacetone was replaced with 16 mg of palladium acetylacetone, wherein the molar ratio of palladium acetylacetone, copper acetylacetone, nickel acetylacetone, ferric chloride hexahydrate and ascorbic acid was 1:0.5:0.5:0.385:3.85.
[0090] Example 6
[0091] The method was implemented according to Example 1, except that 5.4 mg of ferric chloride hexahydrate was replaced with 3.5 mg of ferric chloride hexahydrate, wherein the molar ratio of palladium acetylacetonate, copper acetylacetonate, nickel acetylacetonate, ferric chloride hexahydrate and ascorbic acid was 1:1:1:0.5:7.7.
[0092] Example 7
[0093] The method was implemented according to Example 1, except that 35.6 mg of ascorbic acid was replaced with 22.9 mg of ascorbic acid, wherein the molar ratio of palladium acetylacetonate, copper acetylacetonate, nickel acetylacetonate, ferric chloride hexahydrate and ascorbic acid was 1:1:1:0.77:5.
[0094] Example 8
[0095] The method was carried out according to Example 1, except that 5 mL of oleylamine was replaced with 15 mL of oleylamine.
[0096] Example 9
[0097] The method of Example 1 was carried out, except that the reaction was carried out at 100°C instead of at 200°C in an oil bath.
[0098] Example 10
[0099] The method was carried out according to Example 1, except that 5 mL of oleylamine was replaced with a solution prepared by dissolving 1 g of CTAB in 5 mL of water.
[0100] Comparative Example 1
[0101] Only palladium nanoparticles were prepared, and the conditions were the same as in Example 1, except that 6.9 mg of copper acetylacetone and 6.8 mg of nickel acetylacetone were not added.
[0102] Specific methods include:
[0103] (1) Dissolve 8 mg palladium acetylacetonate, 5.4 mg ferric chloride hexahydrate and 35.6 mg ascorbic acid in 5 mL of oleylamine and sonicate for 60 min. The molar ratio of palladium acetylacetonate, ferric chloride hexahydrate and ascorbic acid is 1:0.77:7.7.
[0104] (2) The mixture obtained in step (1) was heated in an oil bath at 200°C for 12 hours. The gel-like product was collected by centrifugation and then washed three times with a mixture of acetone, ethanol and cyclohexane. The product was dried under vacuum at 60°C for 24 hours.
[0105] Comparative Example 2
[0106] Only palladium-copper bimetallic nanoparticles were prepared.
[0107] Specific methods include:
[0108] (1) Dissolve 8 mg palladium acetylacetonate, 6.9 mg copper acetylacetonate, 5.4 mg ferric chloride hexahydrate and 35.6 mg ascorbic acid in 5 mL of oleylamine and sonicate for 60 min. The molar ratio of palladium acetylacetonate, copper acetylacetonate, ferric chloride hexahydrate and ascorbic acid is 1:1:0.77:7.7.
[0109] (2) The mixture obtained in step (1) was heated in an oil bath at 200°C for 12 hours. The gel-like product was collected by centrifugation and then washed three times with a mixture of acetone, ethanol and cyclohexane. The product was dried under vacuum at 60°C for 24 hours.
[0110] Comparative Example 3
[0111] Only palladium-nickel bimetallic nanoparticles were prepared.
[0112] (1) Dissolve 8 mg palladium acetylacetonate, 6.77 mg nickel acetylacetonate, 5.4 mg ferric chloride hexahydrate, and 35.6 mg ascorbic acid in 5 mL of oleylamine and sonicate for 60 min. The molar ratio of palladium acetylacetonate, nickel acetylacetonate, ferric chloride hexahydrate, and ascorbic acid is 1:1:0.77:7.7.
[0113] (2) The mixture obtained in step (1) was heated in an oil bath at 200°C for 12 hours. The gel-like product was collected by centrifugation and then washed three times with a mixture of acetone, ethanol and cyclohexane. The product was dried under vacuum at 60°C for 24 hours.
[0114] Comparative Example 4
[0115] Only palladium-cobalt bimetallic nanoparticles were prepared.
[0116] (1) Dissolve 8 mg palladium acetylacetonate, 6.83 mg cobalt acetylacetonate, 5.4 mg ferric chloride hexahydrate and 35.6 mg ascorbic acid in 5 mL of oleylamine and sonicate for 60 min. The molar ratio of palladium acetylacetonate, cobalt acetylacetonate, ferric chloride hexahydrate and ascorbic acid is 1:1:0.77:7.7.
[0117] (2) The mixture obtained in step (1) was heated in an oil bath at 200°C for 12 hours. The gel-like product was collected by centrifugation and then washed three times with a mixture of acetone, ethanol and cyclohexane. The product was dried under vacuum at 60°C for 24 hours.
[0118] Comparative Example 5
[0119] Only palladium-zinc bimetallic nanoparticles were prepared.
[0120] (1) Dissolve 8 mg palladium acetylacetonate, 6.95 mg zinc acetylacetonate, 5.4 mg ferric chloride hexahydrate and 35.6 mg ascorbic acid in 5 mL of oleylamine and sonicate for 60 min. The molar ratio of palladium acetylacetonate, zinc acetylacetonate, ferric chloride hexahydrate and ascorbic acid is 1:1:0.77:7.7.
[0121] (2) The mixture obtained in step (1) was heated in an oil bath at 200°C for 12 hours. The gel-like product was collected by centrifugation and then washed three times with a mixture of acetone, ethanol and cyclohexane. The product was dried under vacuum at 60°C for 24 hours.
[0122] Comparative Example 6
[0123] Only palladium-iron bimetallic nanoparticles were prepared.
[0124] (1) Dissolve 8 mg palladium acetylacetone, 9.35 mg iron acetylacetone, 5.4 mg ferric chloride hexahydrate and 35.6 mg ascorbic acid in 5 mL of oleylamine and sonicate for 60 min. The molar ratio of palladium acetylacetone, iron acetylacetone, ferric chloride hexahydrate and ascorbic acid is 1:1:0.77:7.7.
[0125] (2) The mixture obtained in step (1) was heated in an oil bath at 200°C for 12 hours. The gel-like product was collected by centrifugation and then washed three times with a mixture of acetone, ethanol and cyclohexane. The product was dried under vacuum at 60°C for 24 hours.
[0126] Comparative Example 7
[0127] The method was carried out according to Example 1, except that 5.4 mg of ferric chloride hexahydrate was not added.
[0128] Comparative Example 8
[0129] The method was carried out according to Example 1, except that 35.6 mg of ascorbic acid was not added.
[0130] Comparative Example 9
[0131] The method was implemented according to Example 1, except that 6.9 mg of copper acetylacetone was replaced with 9.35 mg of iron acetylacetone, wherein the molar ratio of palladium acetylacetone, iron acetylacetone, nickel acetylacetone, ferric chloride hexahydrate and ascorbic acid was 1:1:1:0.77:7.7.
[0132] Test Example 1
[0133] The molar ratios of the various metals in the materials prepared in the examples and comparative examples were characterized and calculated by inductively coupled plasma mass spectrometry (ICP-MS), and the results are shown in Table 1.
[0134] Table 1
[0135]
[0136]
[0137] Test Example 2
[0138] The materials prepared in the examples and comparative examples were used as hydrogen-sensitive materials to test their hydrogen sensing performance. The instrument used was the CGS-8 intelligent gas-sensitive analysis system from Elite Technologies Inc.
[0139] The testing method included: mixing the materials prepared in the examples and comparative examples with terpineol and coating them onto a hexagonal sensor base, drying and aging them to obtain molded hydrogen-sensitive composite materials. The molded hydrogen-sensitive composite materials were placed in sealed 500mL chambers, and a mixture of dry hydrogen and air was introduced to react, wherein the hydrogen concentration was 1% by volume. All tests were measured at room temperature (25°C) for 100-99999 s. The resistance versus time curve was obtained, and the response time (t) was calculated based on the resistance versus time curve. 90 The average of the five measurements was calculated, and the results are shown in Table 2.
[0140] The resistance-time curves of the materials prepared in Example 1, Comparative Example 1, and Comparative Example 2 are shown below. Figures 2-4 As shown.
[0141] The response time (t90) is the time required for the resistance of the target gas to return to 90% of its initial value after contact with the target gas.
[0142] Table 2
[0143]
[0144]
[0145] As can be seen from the results in Table 2, the material prepared by the method described in this invention has excellent sensing performance and a fast response speed to hydrogen.
[0146] The preferred embodiments of the present invention have been described in detail above; however, the present invention is not limited thereto. Within the scope of the inventive concept, various simple modifications can be made to the technical solutions of the present invention, including combinations of various technical features in any other suitable manner. These simple modifications and combinations should also be considered as the content disclosed in the present invention and are all within the protection scope of the present invention.
Claims
1. A ternary palladium-based nanoparticle material, characterized in that, The ternary palladium-based nanoparticle material contains palladium, copper, and a third metal, and the palladium, copper, and third metal exist in an alloy form, wherein the third metal is at least one of the metal elements in Group IIB and / or Group VIII other than palladium.
2. The ternary palladium-based nanoparticle material according to claim 1, characterized in that, The molar ratio of palladium, copper and the third metal is 1-10:1-10:
1.
3. The ternary palladium-based nanoparticle material according to claim 1 or 2, characterized in that, The particle size of the ternary palladium-based nanoparticle material is 10-100 nm.
4. The ternary palladium-based nanoparticle material according to any one of claims 1-3, characterized in that, The third metal is selected from nickel, cobalt, zinc or iron.
5. A method for preparing ternary palladium-based nanoparticle materials, characterized in that, The method includes reacting a palladium precursor, a copper precursor, a third metal precursor, a morphology control agent, a reducing agent, and a surfactant in the presence of a solvent; The third metal in the third metal precursor is at least one metal element from Group IIB and / or Group VIII, excluding palladium.
6. The method according to claim 5, characterized in that, The molar ratio of palladium precursor, copper precursor, third metal precursor, morphology control agent, and reducing agent is 1:0.1-1:0.1-1:0.5-1:5-20.
7. The method according to claim 5 or 6, characterized in that, The palladium precursor is selected from one or more of palladium acetylacetonate, palladium chloride, and palladium nitrate; Preferably, the copper precursor is selected from one or more of copper acetylacetonate, copper sulfate, and copper nitrate; Preferably, the third metal precursor is selected from nickel acetylacetonate, cobalt acetylacetonate, zinc acetylacetonate, or iron acetylacetonate.
8. The method according to any one of claims 5-7, characterized in that, The morphology control agent is a halide; Preferably, the morphology control agent is selected from one or more of ferric chloride, ferric bromide, potassium fluoride, potassium chloride, potassium bromide, potassium iodide, sodium fluoride, sodium chloride, sodium bromide, and sodium iodide.
9. The method according to any one of claims 5-8, characterized in that, The reducing agent is selected from one or more of ascorbic acid, sodium borohydride, and sodium hypophosphite.
10. The method according to any one of claims 5-9, characterized in that, The surfactant is selected from one or more of CTAB, CTAC, PVP, CPC, SDBS and oleylamine.
11. The method according to any one of claims 5-10, characterized in that, The reaction conditions include a temperature of 100-200℃ and a time of 5-20h.
12. Ternary palladium-based nanoparticle materials prepared by the method according to any one of claims 5-11.
13. The application of the ternary palladium-based nanoparticle material according to any one of claims 1-4 or the ternary palladium-based nanoparticle material according to claim 12 as a hydrogen-sensitive material.
14. A method for testing the performance of a hydrogen sensor, characterized in that, The method includes: placing a hydrogen-sensitive material in a sealed device, introducing a mixed gas containing hydrogen and a protective gas to react, and testing the resistance at different reaction times; wherein the hydrogen-sensitive material contains the ternary palladium-based nanoparticle material as described in any one of claims 1-4 or the ternary palladium-based nanoparticle material as described in claim 12.
15. The method according to claim 14, characterized in that, The hydrogen content in the mixed gas is 0.02-2% by volume; Preferably, the reaction conditions include: a temperature of 15-30°C and a time of 100-3000 s.