Ternary nanowire material coated with one-dimensional Au base on surface as well as preparation method and application of ternary nanowire material
By synthesizing AuPdRu ternary nanowire materials in a homogeneous system, the problems of high cost and low efficiency of existing precious metal catalysts are solved, and a highly efficient and economical catalytic hydrogen evolution effect is achieved in electrolytic water hydrogen production.
Patent Information
- Application Number
- CN202510218213.X
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-02-26
- Publication Date
- 2025-05-30
AI Technical Summary
Among the existing electrolytic water hydrogen production catalysts, the high cost, limited reserves and kinetics of precious metal catalysts limit their large-scale use and lack of cheap and efficient alternative catalysts.
The surface-covered one-dimensional Au-based ternary nanowire material is used. By synthesizing AuPdRu ternary nanowire material in a homogeneous system, it has simple operation and high raw material utilization. The material has a large specific surface area, multiple active sites and good conductivity efficiency.
Showing good catalytic hydrogen evolution properties in acidic and alkaline environments, achieving similar efficiency to precious metal catalysts while reducing costs and material usage.
Smart Images
Figure CN120055280A_ABST
Abstract
Description
Technical Field
[0001] The present invention relates to a surface-coated one-dimensional Au-based ternary nanowire material, a preparation method and an application thereof, belonging to the technical field of preparation of electrolytic water catalysts. Background Art
[0002] In recent years, the overconsumption of traditional fossil fuels and the increasing energy demand have forced people to explore new energy to replace traditional fossil fuels. Hydrogen energy has attracted wide attention due to its high energy density, rich reserves and environmental friendliness. Among various hydrogen production methods, electrolytic water hydrogen production has simple operation and pure products, and at the same time, the oxygen generated at the anode has various uses. At present, the best catalyst for electrolytic water hydrogen production is the Pt-group noble metal catalyst, but its high price, limited reserves and slow kinetics limit its large-scale use. In the long run, it is very important to develop other cheaper and more efficient catalysts.
[0003] Noble metals have always been the most important elements in the field of electrolytic water. They have excellent performance and good long-term stability, but this requires designing a suitable composition and structure to avoid performance degradation caused by material poisoning. Design a suitable catalytic path to reduce the amount of noble metals used. The Au element has good conductivity and excellent compatibility with various noble metal elements, and is very suitable as the substrate of the catalyst material, and then coated with other metals to improve the catalytic activity. At present, there are few such coating materials, and it is urgent to develop and research. Summary of the Invention
[0004] Aiming at the deficiencies of the prior art, the purpose of the present invention is to provide a surface-coated one-dimensional Au-based ternary nanowire material, a preparation method and an application thereof. This method has simple operation, mild reaction conditions, is easy for mass production, and the synthesized nanowires have special electronic structures, many active sites, good mass transfer effects, high conductivity efficiency and other advantages.
[0005] To solve the problems of the prior art, the technical solution adopted by the present invention is:
[0006] A preparation method of a surface-coated one-dimensional Au-based ternary nanowire material, comprising the following steps:
[0007] Step 1, preparing an Au nanowire precursor;
[0008] Step 2, preparing a binary nanowire solution of Au
[0009] Using water and ethanol as solvents, adding an Au nanowire precursor and a metal source 1, using L-ascorbic acid as a reducing agent and PVP as a morphology guiding agent, after holding the reaction in a water bath, separating the precipitate, and then washing successively with absolute ethanol and ethylene glycol, and then adding ethylene glycol as a solvent to obtain a binary nanowire solution of Au;
[0010] Step 3: Prepare an ethylene glycol solution of metal source 2; add L-ascorbic acid as a reducing agent and PVP as a morphology-directing agent to the binary Au nanowire solution, heat it to a set temperature in an oil bath, add the ethylene glycol solution of metal source 2 uniformly with a syringe pump, after keeping warm for a period of time, the separated black solid is ultrasonically washed with absolute ethanol for multiple times to obtain the AuPdRu ternary nanowire material.
[0011] As an improvement, the specific steps for preparing the Au nanowire precursor in Step 1 are as follows: Take a solution of equal volume mixture of water and ethanol as a dispersant, add an ethanol solution of 1-naphthol as a reducing agent, and HAuCl 4 solution as the Au source, shake and mix evenly, keep warm at 60 °C for 2 h, centrifuge and separate, and ultrasonically wash with absolute ethanol 6 times to obtain the Au nanowire precursor.
[0012] As an improvement, the volume of ethanol in the water and ethanol mixed solution in Step 2 is 50%.
[0013] As an improvement, the metal source 1 in Step 2 is PdCl 2 When it is, the metal source 2 is Ru(AcAc) 3 When the metal source 1 is RuCl 3 When it is, the metal source 2 is Pd(AcAc) 2 .
[0014] As an improvement, the water bath temperature in Step 2 is 60 °C and the water bath time is 6 hours.
[0015] As an improvement, the oil bath temperature in Step 3 is 200 °C and the oil bath time is 6 hours.
[0016] The surface-coated one-dimensional Au-based ternary nanowire material prepared by any of the above preparation methods is uniform in thickness, with a diameter of 15 - 20 nm and a length of 300 - 500 nm.
[0017] Application of the above surface-coated one-dimensional Au-based ternary nanowire material in electrolytic water catalysis.
[0018] Beneficial effects:
[0019] Compared with the prior art, for a surface-coated one-dimensional Au-based ternary nanowire material, its preparation method and application in the present invention, the AuPdRu ternary nanowire material synthesized in a homogeneous system is adopted, with simple operation and the raw material utilization rate approaching 100%. The prepared AuPdRu ternary nanowire material has advantages such as a large specific surface area, many active sites, and good flexibility, and shows good catalytic hydrogen evolution performance in both acidic environments with pH = 0 and alkaline environments with pH = 14. Description of the Drawings
[0020] Figure 1 It is the TEM image of the AuPdRu ternary nanowires prepared in Example 1;
[0021] Figure 2 It is the TEM image of the Au nanowire precursor prepared in Example 1;
[0022] Figure 3 It is the TEM image of the AuRu binary nanowires prepared in Comparative Example 2;
[0023] Figure 4 It is the TEM image of the AuPd binary nanowires prepared in Comparative Example 3;
[0024] Figure 5 It is the EDS image of the intermediate AuPd binary nanowires prepared by the method of Example 1;
[0025] Figure 6 It is the acidic hydrogen evolution performance test image of the Au-based multi-component nanowires prepared by the methods of Example 1, Comparative Example 2, and Comparative Example 3;
[0026] Figure 7 It is the alkaline hydrogen evolution performance test image of the Au-based multi-component nanowires prepared by the methods of Example 1, Comparative Example 2, and Comparative Example 3. Specific implementation method
[0028] The technical solutions of the present invention are further described in detail below through specific examples.
[0029] Example 1
[0030] A preparation method of an AuPdRu ternary nanowire material, comprising the following steps:
[0031] 1) Preparation of the reaction solution:
[0032] Preparation of the Au nanowire precursor: Measure 3 mL of a solution of equal volume of water and ethanol as a dispersant, add 0.5 mL of a 0.5 mol / L ethanol solution of 1-naphthol as a reducing agent, and 0.5 mL of a 0.05 mol / L HAuCl 4 solution as the Au source, shake and mix evenly, and keep warm at 60 °C for 2 h. Centrifuge and separate, and ultrasonically wash 6 times with absolute ethanol to obtain the Au nanowire precursor.
[0033] Take the above Au nanowire precursor and add it to 15 ml of a solvent of equal volume of water and ethanol, and add 0.2 mL of a 0.05 mol / L PdCl 2Solution: 1 mL of 0.1 mol / L L-ascorbic acid solution, 30 mg of PVP (MW = 30000), were fully dissolved and dispersed evenly, and placed in a water bath at 60 °C for 6 h. The black solid was separated, ultrasonically washed 3 times with absolute ethanol and once with ethylene glycol, and then dissolved in 10 mL of ethylene glycol to obtain a binary nanowire solution of Au;
[0034] 2) Preparation of AuPdRu ternary nanowires:
[0035] Take 12 mg of Ru(AcAc) 3 Dissolve it in 7.5 mL of ethylene glycol to obtain a Ru(AcAc) 3 solution; Add 100 mg of L-ascorbic acid solid and 30 mg of PVP (MW = 30000) to the binary nanowire solution of Au, fully dissolve and disperse evenly. Place the mixed solution in an oil bath, and after heating to 200 °C, use a syringe pump to uniformly add the Ru(AcAc) 3 solution to the binary nanowire solution of Au. The addition was completed in 4 h, and after keeping warm for 2 h, the separated black solid was ultrasonically washed 3 times with absolute ethanol to obtain the Au@Pd@Ru ternary nanowires.
[0036] Example 2
[0037] A preparation method of an AuPdRu ternary nanowire material, comprising the following steps:
[0038] 1) Preparation of the reaction solution:
[0039] Prepare the Au nanowire precursor: Measure 3 mL of a solution obtained by mixing water and ethanol in equal volumes as a dispersant, add 0.5 mL of a 0.5 mol / L ethanol solution of 1-naphthol as a reducing agent, and 0.5 mL of a 0.05 mol / L HAuCl 4 solution as the Au source, shake and mix evenly, and keep warm at 60 °C for 2 h. Centrifuge and ultrasonically wash 6 times with absolute ethanol to obtain the Au nanowire precursor.
[0040] Take the above Au nanowire precursor and add it to 15 ml of a solvent obtained by mixing water and ethanol in equal volumes, add 0.2 mL of a 0.05 mol / L RuCl 3 solution, 1 mL of 0.1 mol / L L-ascorbic acid solution, 30 mg of PVP (MW = 30000), fully dissolve and disperse evenly, and place in a water bath at 60 °C for 6 h. The black solid was separated, ultrasonically washed 3 times with absolute ethanol and once with ethylene glycol, and then dissolved in 10 mL of ethylene glycol to obtain a binary nanowire solution of Au;
[0041] 2) Preparation of AuPdRu ternary nanowires:
[0042] Take 9 mg of Pd(AcAc). 2 Dissolve it in 7.5 mL of ethylene glycol to obtain a Pd(AcAc) 2 solution; add 100 mg of L-ascorbic acid solid and 30 mg of PVP (MW = 30000) to the binary nanowire solution of Au, dissolve and disperse them evenly. Place the mixed solution in an oil bath, heat it to 200 °C, and then use a syringe pump to uniformly add the Pd(AcAc) 2 solution to the binary nanowire solution of Au at a constant speed. After the addition is completed in 4 h, keep it warm for another 2 h, and then ultrasonically wash the separated black solid with absolute ethanol three times to obtain the Au@Ru@Pd ternary nanowires.
[0043] Comparative Example 1
[0044] A preparation method of an AuPd binary nanowire material includes the following steps:
[0045] 1) Preparation of the reaction solution:
[0046] Prepare the Au nanowire precursor: Measure 3 mL of a solution obtained by mixing water and ethanol in equal volumes as a dispersant, add 0.5 mL of a 0.5 mol / L ethanol solution of 1-naphthol as a reducing agent, and 0.5 mL of a 0.05 mol / L HAuCl 4 solution as the Au source, shake and mix evenly, and keep it warm at 60 °C for 2 h. Centrifuge and ultrasonically wash with absolute ethanol six times to obtain the Au nanowire precursor.
[0047] Take the above Au nanowire precursor, wash it once with ethylene glycol and then dissolve it in 10 ml of ethylene glycol, add 100 mg of L-ascorbic acid solid and 30 mg of PVP (MW = 30000), and dissolve and disperse them evenly.
[0048] 2) Preparation of the AuPd binary nanowires:
[0049] Take 9 mg of Pd(AcAc). 2 Dissolve it in 7.5 mL of ethylene glycol to obtain a Pd(AcAc) 2 solution. Place the mixed solution in an oil bath and heat it to 200 °C. Use a syringe pump to uniformly add the Pd(AcAc) 2 solution to the mixed solution at a constant speed. After the addition is completed in 4 h, keep it warm for another 2 h, and then ultrasonically wash the separated black solid with absolute ethanol three times to obtain the AuPd binary nanowires.
[0050] Comparative Example 2
[0051] A preparation method of an AuRu binary nanowire material includes the following steps:
[0052] 1) Preparation of the reaction solution:
[0053] Preparation of Au nanowire precursor: Measure 3 mL of a solution obtained by mixing water and ethanol in equal volumes as a dispersant, add 0.5 mL of an ethanol solution of 0.5 mol / L 1-naphthol as a reducing agent, and 0.5 mL of a HAuCl 4 solution as the Au source, shake and mix evenly, and keep warm at 60 °C for 2 h. Centrifuge and separate, and ultrasonically wash with absolute ethanol 6 times to obtain the Au nanowire precursor.
[0054] Take the above Au nanowire precursor, wash it once with ethylene glycol and then dissolve it in 10 mL of ethylene glycol, add 100 mg of L-ascorbic acid solid and 30 mg of PVP (MW = 30000), and fully dissolve and disperse evenly.
[0055] 2) Preparation of AuRu binary nanowires:
[0056] Take 12 mg of Ru(AcAc) 3 and dissolve it in 7.5 mL of ethylene glycol to obtain a Ru(AcAc) 3 solution. Place the mixed solution in an oil bath and heat it to 200 °C. Use a syringe pump to uniformly add the Ru(AcAc) 3 solution to the mixed solution. Finish dropping in 4 h, and then keep warm for 2 h. The separated black solid is ultrasonically washed three times with absolute ethanol to obtain the AuRu binary nanowires.
[0057] Comparative Example 3
[0058] A preparation method of an AuPd binary nanowire material, comprising the following steps:
[0059] 1) Preparation of the reaction solution:
[0060] Preparation of Au nanowire precursor: Measure 3 mL of a solution obtained by mixing water and ethanol in equal volumes as a dispersant, add 0.5 mL of an ethanol solution of 0.5 mol / L 1-naphthol as a reducing agent, and 0.5 mL of a 0.05 mol / L HAuCl 4 solution as the Au source, shake and mix evenly, and keep warm at 60 °C for 2 h. Centrifuge and separate, and ultrasonically wash with absolute ethanol 6 times to obtain the Au nanowire precursor.
[0061] Take the above Au nanowire precursor and add it to a solvent obtained by mixing 15 mL of water and ethanol in equal volumes, add 0.2 mL of a 0.05 mol / L PdCl 2 solution, 1 mL of a 0.1 mol / L L-ascorbic acid solution, and 30 mg of PVP (MW = 30000), and fully dissolve and disperse evenly.
[0062] 2) Preparation of AuPd binary nanowires:
[0063] Place the prepared reaction solution in a water bath at 60 °C and keep it warm for 6 h. Separate to obtain a black solid, and ultrasonically wash it 3 times with absolute ethanol to obtain AuPd binary nanowires.
[0064] Comparative Example 4
[0065] A preparation method of an AuRu binary nanowire material, comprising the following steps:
[0066] 1) Preparation of the reaction solution:
[0067] Prepare the Au nanowire precursor: Measure 3 mL of a solution of equal volume of water and ethanol as a dispersant, add 0.5 mL of a 0.5 mol / L ethanol solution of 1-naphthol as a reducing agent, and 0.5 mL of a 0.05 mol / L HAuCl 4 solution as the Au source, shake and mix evenly, and keep it warm at 60 °C for 2 h. Centrifuge and separate, and ultrasonically wash 6 times with absolute ethanol to obtain the Au nanowire precursor.
[0068] Take the above Au nanowire precursor and add it to a solvent of 15 mL of equal volume of water and ethanol, add 0.2 mL of a 0.05 mol / L RuCl 3 solution, 1 mL of a 0.1 mol / L L-ascorbic acid solution, and 30 mg of PVP (MW = 30000), and dissolve and disperse evenly.
[0069] 2) Preparation of AuRu binary nanowires:
[0070] Place the prepared reaction solution in a water bath at 60 °C and keep it warm for 6 h. Separate to obtain a black solid, and ultrasonically wash it 3 times with absolute ethanol to obtain AuRu binary nanowires.
[0071] Comparative Example 5
[0072] A preparation method of an AuPdRu ternary nanowire material, comprising the following steps:
[0073] 1) Preparation of the reaction solution:
[0074] Prepare the Au nanowire precursor: Measure 3 mL of a solution of equal volume of water and ethanol as a dispersant, add 0.5 mL of a 0.5 mol / L ethanol solution of 1-naphthol as a reducing agent, and 0.5 mL of a 0.05 mol / L HAuCl 4 solution as the Au source, shake and mix evenly, and keep it warm at 60 °C for 2 h. Centrifuge and separate, and ultrasonically wash 6 times with absolute ethanol to obtain the Au nanowire precursor.
[0075] Take the above Au nanowire precursor, wash it once with ethylene glycol and then dissolve it in 10 ml of ethylene glycol. Add 100 mg of L-ascorbic acid solid and 30 mg of PVP (MW = 30000), and dissolve and disperse them evenly.
[0076] 2) Preparation of AuPdRu ternary nanowires:
[0077] Take 9 mg of Pd(AcAc) 2 Dissolve it in 7.5 mL of ethylene glycol to obtain a Pd(AcAc) 2 solution, and dissolve 12 mg of Ru(AcAc) 3 in 7.5 mL of ethylene glycol to obtain a Ru(AcAc) 3 solution. Place the mixed solution in an oil bath and heat it to 200 °C. Use a syringe pump to uniformly add the Pd(AcAc) 2 solution and the Ru(AcAc) 3 solution to the mixed solution. The addition is completed in 4 h. After keeping warm for 2 h, the separated black solid is ultrasonically washed three times with absolute ethanol to obtain the AuPdRu ternary nanowires.
[0078] Use SEM, TEM, EDS and other methods to physically characterize the samples prepared in the above examples and comparative examples. From Figure 1 (a), Figure 1 (b), it can be seen that for the surface-coated one-dimensional Au-based nanowires of the present invention, while maintaining the one-dimensional linear morphological characteristics, a lot of Pd and Ru metal particles are attached to the surface, with a large specific surface area and many active sites.
[0079] Figure 2 It shows that the surface of the Au nanowire precursor is smooth, and the diameter is significantly lower than Figure 1 , proving that other metals are reductively coated on the surface of the Au nanowires to form multi-metal nanowires.
[0080] Figure 3 、 Figure 4 are the materials prepared in Comparative Example 2 and Comparative Example 3 respectively. It can be seen from the figure that the morphology of the products synthesized under the water bath is slightly different from that of the products synthesized under the oil bath. The metal particles grown by water bath reduction are larger, and the metals grown by oil bath reduction are relatively smaller. Combining with the information fed back in Figure 1 , it can be known that the present invention prepares the three metals under a specific process, first growing larger metal particles on the surface of the Au nanowires and then growing smaller metal particles. The obtained material not only increases the specific surface area but also improves the surface coverage of the active metal, thus improving the catalytic performance of the sample.
[0081] Figure 5EDS spectrum of the intermediate product AuPd binary nanowires prepared by the method of Example 1, indicating that the elemental composition of the product meets the expectation, and Pd is reductively grown on the surface of Au nanowires.
[0082] Figure 6 , Figure 7 respectively indicate that the materials of the present invention have good hydrogen evolution catalytic performance under acidic conditions and alkaline conditions. At pH = 0 and a current density of 40 mA cm -2 , the overpotential is only 0.07 V; at pH = 14 and a current density of 40 mA cm -2 , the overpotential is only 0.19 V.
[0083] In summary, for a surface-coated one-dimensional Au-based ternary nanowire material, its preparation method and application of the present invention, the AuPdRu ternary nanowire material synthesized in a homogeneous system is adopted, with simple operation and a raw material utilization rate close to 100%. The prepared AuPdRu ternary nanowire material has advantages such as a large specific surface area, many active sites, and good flexibility, and shows good catalytic hydrogen evolution performance in an acidic environment with pH = 0 and an alkaline environment with pH = 14.
[0084] The above schematically describes the present invention and its implementation manners, and this description is not restrictive. What is shown in the drawings is only one of the implementation manners of the present invention, and the actual structure is not limited thereto. Therefore, if those of ordinary skill in the art are inspired by it and design similar structural manners and embodiments to this technical solution without creative work without departing from the gist of the present invention, they shall fall within the protection scope of the present invention.
Claims
1. A method for preparing a surface-coated one-dimensional Au-based ternary nanowire material, characterized in that: The following steps are involved: Step 1, preparing Au nanowire precursor; Step 2: Preparation of Au binary nanowire solution Using water and ethanol as solvents, adding Au nanowire precursor and metal source 1, using L-ascorbic acid as a reducing agent, and PVP as a morphology directing agent, after heat preservation reaction in a water bath, separating the precipitate, and then washing with anhydrous ethanol and ethylene glycol in sequence, and then adding ethylene glycol as a solvent to obtain a binary Au nanowire solution; Step 3, prepare an ethylene glycol solution of metal source 2; add L-ascorbic acid as a reducing agent and PVP as a morphology directing agent to the Au binary nanowire solution, heat it to a set temperature under an oil bath, add the ethylene glycol solution of metal source 2 at a uniform speed using a syringe pump, keep warm for a period of time, and separate the obtained black solid and ultrasonically wash it several times with anhydrous ethanol to obtain AuPdRu ternary nanowire material.
2. The method for preparing a surface-coated one-dimensional Au-based ternary nanowire material according to claim 1, characterized in that: The specific steps for preparing the Au nanowire precursor in step 1 are as follows: take a solution of equal volumes of water and ethanol as a dispersant, add an ethanol solution of 1-naphthol as a reducing agent, and a HAuCl4 solution as an Au source, shake and mix evenly, keep warm at 60°C for 2h, centrifuge, and ultrasonically wash with anhydrous ethanol for 6 times to obtain an Au nanowire precursor.
3. The method for preparing a surface-coated one-dimensional Au-based ternary nanowire material according to claim 1, characterized in that: The volume of ethanol in the mixed solution of water and ethanol in step 2 is 50%.
4. The method for preparing a surface-coated one-dimensional Au-based ternary nanowire material according to claim 1, characterized in that: In step 2, when the metal source 1 is PdCl2, the metal source 2 is Ru(AcAc)3; when the metal source 1 is RuCl3, the metal source 2 is Pd(AcAc)2.
5. The method for preparing a surface-coated one-dimensional Au-based ternary nanowire material according to claim 1, characterized in that: The water bath temperature in step 2 is 60° C., and the water bath time is 6 hours.
6. The method for preparing a surface-coated one-dimensional Au-based ternary nanowire material according to claim 1, characterized in that: In step 3, the oil bath temperature is 200° C. and the oil bath time is 6 hours.
7. The surface-coated one-dimensional Au-based ternary nanowire material prepared by the preparation method according to any one of claims 1 to 6, characterized in that: The surface-coated one-dimensional Au-based ternary nanowire material has uniform thickness, a diameter of 15-20 nm, and a length of 300-500 nm.
8. Use of the surface-coated one-dimensional Au-based ternary nanowire material according to claim 7 in water electrolysis catalysis.