A general method for the preparation of multi-element alloy nanoparticles
A chemical reduction method catalyzed by a gold catalyst was used to prepare multi-element alloy nanoparticles at room temperature and pressure. This method solved the problem of uniform fusion of multi-element alloys at the nanoscale, simplified the process, reduced energy consumption and resource waste, and is suitable for applications in multiple fields.
Patent Information
- Application Number
- CN202510109396.1
- Authority / Receiving Office
- CN · China
- Patent Type
- Patents(China)
- Current Assignee / Owner
- Filing Date
- 2025-01-23
- Publication Date
- 2025-11-11
- Estimated Expiration
- 2045-01-23
AI Technical Summary
Existing technologies struggle to achieve uniform fusion of multi-element alloys at the nanoscale, and the preparation process requires high temperature, high-energy impact, or strong reducing environments, which limits the application environment and increases energy consumption. There is also a lack of mild and convenient batch synthesis methods.
Multi-element alloy nanoparticles were prepared by chemical reduction under ambient temperature and pressure using gold catalysts to catalyze the breaking of chemical bonds and electrostatic adsorption of other metal precursors. The metal precursors were used as reducing agents, simplifying the process to four steps, including mixing, settling, washing and centrifugation.
It achieves uniform mixing and efficient preparation of multi-element alloy nanoparticles, applicable to various element combinations, reducing resource waste and production costs, and is suitable for fields such as catalysis, energy storage, electronic devices and biomedicine, with broad compatibility and environmental friendliness.
Smart Images
Figure CN119839304B_ABST
Abstract
Description
Technical Field
[0001] This invention relates to the field of nanomaterials technology, and in particular to a general method for preparing multi-element alloy nanoparticles. Background Technology
[0002] The design and development of new materials are crucial for advancing various applications, and the emergence of multi-element alloys has effectively broadened the design and exploration space for current materials. In traditional metallic materials, the properties are largely determined by their primary elements. To overcome this limitation, scientists proposed the concept of multi-element alloys. A multi-element alloy is an alloy material containing four or more metallic elements. Generally, these elements need to be uniformly distributed within the alloy and form a single-phase or amorphous solid solution structure. Compared to elemental metals, multi-element alloys possess superior optical, electrical, magnetic, and mechanical properties due to the complex interactions between the elements (the cocktail effect). This allows multi-element alloys to be applied in various fields, such as catalysis, plasma physics, bioimaging, drug therapy, and electronic devices.
[0003] Traditional techniques for preparing bulk multi-element alloys are well-established; therefore, the current research bottleneck lies in achieving the uniform fusion of multiple elements at the nanoscale. Scientists have proposed various methods for preparing multi-element alloy nanoparticles, such as carbothermal shock, laser shock, physical deposition, and hydrothermal methods. These methods all require high temperatures, high-energy shocks, or strong reducing environments because different metal elements have different melting points, enthalpies of mixing, and reduction potentials, necessitating extreme experimental conditions to overcome the energy barrier in multi-element alloy formation. However, this also limits the application environment and yield of these methods, and increases energy consumption and carbon emissions in practical applications. Therefore, there is an urgent need in this field to develop a milder and more convenient preparation technique for the mass synthesis of multi-element alloy nanoparticles.
[0004] Gold is a unique metallic element with the highest electronegativity among metals (2.54), and it is one of the few metallic elements with a stable -1 valence. Researchers have discovered that gold can serve as a catalyst in the synthesis of other materials. For example, in the synthesis of nanoparticles or clusters, after reducing the gold precursor with a reducing agent, gold seed crystals can catalyze the subsequent reduction of the gold precursor or other metal precursors. However, despite the promising applications of gold-based catalysis, many challenges remain to be addressed, and a process for preparing multi-element alloy nanoparticles using gold as a catalyst is still lacking. Summary of the Invention
[0005] To overcome the aforementioned problems in the prior art, the present invention aims to provide a universal method for preparing multi-element alloy nanoparticles. This method utilizes the catalytic effect of gold on the breaking of chemical bonds and electron redistribution in other metal precursor molecules, as well as the electrostatic adsorption of other metal elements by gold, to prepare multi-element alloy nanoparticles. This method improves upon the reduction step in existing gold-catalyzed nanoparticle synthesis processes by directly using metal precursors as reducing agents for gold precursors, reducing impurity introduction, and achieving the synthesis of multi-element alloy nanoparticles at room temperature and pressure.
[0006] To achieve the above objectives, the present invention adopts the following technical solution:
[0007] A general method for preparing multi-element alloy nanoparticles includes the following steps:
[0008] S1 prepares a precursor material solution by preparing a precursor of gold as the main catalyst, at least one reducing agent metal precursor, and one or more metal precursors that can be incorporated by electrostatic interaction.
[0009] S2. Mix the precursor material solutions obtained in step S1 evenly to obtain a mixture;
[0010] S3. Let the mixture obtained in step S2 stand for 3 to 24 hours until colloidal particles or precipitates are observed in the mixture.
[0011] S4 washes the settled solution obtained in step S3 with hot water and hot anhydrous ethanol respectively by centrifugation to obtain multi-element alloy nanoparticles.
[0012] Furthermore, the precursor of the main catalyst gold is AuCl3.
[0013] Furthermore, the reducing agent metal precursor includes VCl3, CrCl3, MnCl2, MoCl5, RuCl3, RhCl3, PdCl2, ReCl3, and IrCl4.
[0014] Furthermore, the metal precursors that can be incorporated through electrostatic interaction include ScCl3, FeCl3, CoCl2, NiCl2, CuCl2, ZnCl2, YCl3, ZrCl4, NbCl5, TaCl5, WCl6, and PtCl4.
[0015] Furthermore, in step S1, the concentration of each precursor material solution is arbitrary.
[0016] Furthermore, in step S4, the solution obtained after standing in step S3 is washed at least three times with hot water and hot anhydrous ethanol, respectively.
[0017] Compared with the prior art, the present invention has the following beneficial effects:
[0018] 1) The preparation method of this invention is not limited by the types and quantities of elements, and can flexibly prepare multi-element alloy nanoparticles with various element combinations. Whether binary, ternary, or multi-element alloys, and whether using common or rare elements, this method can successfully prepare them. In contrast, existing technologies often only target specific combinations of elements, resulting in extremely limited applicability. The versatility of this method provides ample space for the research and innovation of new materials, and can meet the diverse needs of different fields for multi-element alloy nanoparticles.
[0019] 2) The multi-element alloy nanoparticles prepared by the method of this invention exhibit excellent performance in various application scenarios. Whether in catalysis, energy storage, electronic devices, or biomedicine, the nanoparticles prepared by this method can meet the corresponding performance requirements without the need to develop specific preparation processes for different application scenarios. This broad compatibility makes this preparation method more practical and competitive in the market.
[0020] 3) The method of this invention improves the reduction step in the existing synthesis process of gold-catalyzed nanoparticles by directly using a metal precursor as a reducing agent for the gold precursor, reducing the introduction of impurities and achieving the synthesis of multi-element alloy nanoparticles at room temperature and pressure. Furthermore, most of the raw materials used and byproducts generated during the preparation process have good recycling value. Through simple separation and processing, unreacted raw materials and byproducts can be recycled and reused. This not only reduces resource waste but also further lowers production costs, achieving the dual goals of efficient resource utilization and environmental friendliness.
[0021] 4) The preparation method of this invention eliminates the cumbersome pretreatment and posttreatment steps in the prior art, and the process flow is simple and clear. Traditional methods often involve complex operations, while the method of this invention simplifies the steps to four, reducing the number of operation steps and lowering the probability of errors caused by complex operations. The process flow is user-friendly and convenient. Attached Figure Description
[0022] Figure 1 These are SEM and EDS images (scale bar is 200 nm) of the AuMoNbZrSc multi-element alloy nanoparticles prepared in Example 1 of this invention.
[0023] Figure 2 This is the XRD pattern of the AuMoNbZrSc multi-element alloy nanoparticles prepared in Example 1 of this invention.
[0024] Figure 3 This is an XPS image of the AuMoNbZrSc multi-element alloy nanoparticles prepared in Example 1 of this invention.
[0025] Figure 4 These are SEM and EDS images (scale bar is 200 nm) of the AuMoTaWZn multi-element alloy nanoparticles prepared in Example 2 of this invention.
[0026] Figure 5 This is the XRD pattern of the AuMoTaWZn multi-element alloy nanoparticles prepared in Example 2 of this invention.
[0027] Figure 6 This is an XPS image of the AuMoTaWZn multi-element alloy nanoparticles prepared in Example 2 of this invention.
[0028] Figure 7 These are SEM and EDS images (scale bar is 200 nm) of the AuIrPtPdRu multi-element alloy nanoparticles prepared in Example 3 of this invention.
[0029] Figure 8 This is the XRD pattern of the AuIrPtPdRu multi-element alloy nanoparticles prepared in Example 3 of this invention.
[0030] Figure 9 This is an XPS image of the AuIrPtPdRu multi-element alloy nanoparticles prepared in Example 3 of this invention. Detailed Implementation
[0031] To make the objectives, technical solutions, and advantages of this invention clearer, the invention will be further described in detail below with reference to embodiments and accompanying drawings. It should be understood that the specific embodiments described herein are merely illustrative of the invention, and the invention is not limited thereto.
[0032] This invention provides a general method for preparing multi-element alloy nanoparticles, comprising the following steps:
[0033] S1 prepares a precursor material solution by preparing a precursor of gold as the main catalyst, at least one reducing agent metal precursor, and one or more metal precursors that can be incorporated by electrostatic interaction.
[0034] S2. Mix the precursor material solutions obtained in step S1 evenly to obtain a mixture;
[0035] S3. Let the mixture obtained in step S2 stand for 3 to 24 hours until colloidal particles or precipitates are observed in the mixture.
[0036] S4 washes the settled solution obtained in step S3 with hot water and hot anhydrous ethanol respectively by centrifugation to obtain multi-element alloy nanoparticles.
[0037] The precursor of the main catalyst, gold, is AuCl3.
[0038] Preferably, the reducing agent metal precursor includes VCl3, CrCl3, MnCl2, MoCl5, RuCl3, RhCl3, PdCl2, ReCl3, and IrCl4.
[0039] Preferably, the metal precursors that can be incorporated via electrostatic interaction include ScCl3, FeCl3, CoCl2, NiCl2, CuCl2, ZnCl2, YCl3, ZrCl4, NbCl5, TaCl5, WCl6, and PtCl4, wherein the Cu, W, and Pt precursors can be reduced under the catalysis of Au. The concentration of each precursor material solution is arbitrary. Theoretically, the reaction can occur regardless of the concentration; the solution concentration or the amount of precursor material only affects the yield of the generated particles.
[0040] Example 1
[0041] This embodiment provides a method for preparing AuMoNbZrSc multi-element alloy nanoparticles, which includes the following steps:
[0042] S1 prepared AuCl3, MoCl5, NbCl5, ZrCl4 and ScCl3 into precursor material solutions with a concentration of 4 mmol / L. The solvent used in the preparation of each precursor material solution was water or anhydrous ethanol, as long as the solute used was soluble in the solvent.
[0043] S2. Add 1 mL each of the 4 mmol / L precursor material solutions AuCl3, MoCl5, NbCl5, ZrCl4 and ScCl3 obtained in step S1 to a beaker, stir for 10 min to mix the precursor material solutions evenly, and obtain a mixture.
[0044] S3. Let the mixture obtained in step S2 stand for 24 hours.
[0045] S4 uses centrifugation to wash the settled solution obtained in step S3 with ultrapure water at 60℃ and anhydrous ethanol at 60℃ respectively. The supernatant is discarded, and the precipitate obtained is AuMoNbZrSc multi-element alloy nanoparticles.
[0046] The SEM and EDS images of the AuMoNbZrSc multi-element alloy nanoparticles prepared in this embodiment are as follows: Figure 1 As shown, the particles are spherical, and it can be observed that each element is uniformly distributed in the particles, proving that the elements are uniformly mixed. Figure 2 and 3The XRD and XPS spectra of the AuMoNbZrSc multi-element alloy nanoparticles prepared in this embodiment are shown in the figures. The XRD results show that the AuMoNbZrSc multi-element alloy nanoparticles are single-phase alloy nanoparticles, and the single-phase structure is a characteristic structure of multi-element alloys. The crystal structure of the AuMoNbZrSc multi-element alloy nanoparticles is fcc, consistent with the crystal structure of pure Au. Simultaneously, the XRD shows a slight change in lattice parameters (peak shift), which proves that Au, as the host structure, enables the uniform mixing of multiple metal elements, resulting in lattice distortion. The XPS results show the valence states of each element: Au(0), Mo(+6), Nb(+5), Zr(+4), and Sc(+3). It can be observed that the valence states of Au and Mo changed, proving that their precursors underwent redox reactions, with MoCl5 donating electrons; while the valence states of Nb, Zr, and Sc remained unchanged, proving that the three elements were incorporated into the multi-element alloy nanoparticles through electrostatic adsorption.
[0047] Example 2
[0048] This embodiment provides a method for preparing AuMoTaWZn multi-element alloy nanoparticles, which includes the following steps:
[0049] S1 prepared precursor material solutions of AuCl3, MoCl5, TaCl5, WCl6 and ZnCl2 with a concentration of 5 mmol / L. The solvent used in the preparation of each precursor material solution was water or anhydrous ethanol, as long as the solute used was soluble in the solvent.
[0050] S2. Add 1 mL each of the 5 mmol / L precursor material solutions AuCl3, MoCl5, TaCl5, WCl6 and ZnCl2 obtained in step S1 to a beaker, stir for 10 min to mix the precursor material solutions evenly, and obtain a mixed solution.
[0051] S3. Let the mixture obtained in step S2 stand for 24 hours.
[0052] S4 uses centrifugation to wash the settled solution obtained in step S3 with ultrapure water at 60℃ and anhydrous ethanol at 60℃ respectively. The supernatant is discarded, and the precipitate obtained is AuMoTaWZn multi-element alloy nanoparticles.
[0053] The SEM and EDS images of the AuMoTaWZn multi-element alloy nanoparticles prepared in this embodiment are as follows: Figure 4 As shown, the particles are spherical, and it can be observed that each element is uniformly distributed in the particles, proving that the elements are uniformly mixed. Figure 5 and 6The XRD and XPS spectra of the AuMoTaWZn multi-element alloy nanoparticles prepared in this embodiment are shown in the figures. The XRD results show that the AuMoTaWZn multi-element alloy nanoparticles are single-phase alloy nanoparticles, and the single-phase structure is a characteristic structure of multi-element alloys. The crystal structure of the AuMoTaWZn multi-element alloy nanoparticles is fcc, consistent with the crystal structure of pure Au. Simultaneously, the XRD shows a slight change in lattice parameters (peak shift), which proves that Au, as the host structure, enables the uniform mixing of multiple metal elements, resulting in lattice distortion. The XPS results show the valence states of each element: Au(0), Mo(+6), Ta(+5), W(+4), and Sc(Zn). It can be observed that the valence states of Au, Mo, and W changed, proving that their precursors underwent redox reactions, with MoCl5 donating electrons and Au and W gaining electrons; while the valence states of Ta and Zn remained unchanged, proving that they were incorporated into the multi-element alloy nanoparticles through electrostatic adsorption.
[0054] Example 3
[0055] This embodiment provides a method for preparing AuIrPtPdRu multi-element alloy nanoparticles, which includes the following steps:
[0056] S1 prepared AuCl3, IrCl4, PtCl4, PdCl2 and RuCl3 into AuCl3 solution with a concentration of 5 mmol / L, IrCl4 solution with a concentration of 1 mmol / L, PtCl4 solution with a concentration of 2 mmol / L, PdCl2 solution with a concentration of 2 mmol / L and RuCl3 solution with a concentration of 5 mmol / L, respectively. The solvent used in the preparation of each precursor material solution is water or anhydrous ethanol, as long as the solute used is soluble in the solvent.
[0057] S2. Add 1 mL of LauCl3 solution, 4 mL of IrCl4 solution, 2 mL of PtCl4 solution, 2 mL of PdCl2 solution, and 5 mL of RuCl3 solution obtained in step S1 to a beaker, and stir for 10 min to mix the precursor material solutions evenly to obtain a mixture.
[0058] S3. Let the mixture obtained in step S2 stand for 8 hours.
[0059] S4 uses centrifugation to wash the settled solution obtained in step S3 with ultrapure water at 60℃ and anhydrous ethanol at 60℃ respectively. The supernatant is discarded, and the precipitate obtained is AuIrPtPdRu multi-element alloy nanoparticles.
[0060] The SEM and EDS images of the AuIrPtPdRu multi-element alloy nanoparticles prepared in this embodiment are as follows: Figure 7As shown, the particles are spherical, and it can be observed that each element is uniformly distributed in the particles, proving that the elements are uniformly mixed. Figure 8 and 9 The XRD and XPS spectra of the AuIrPtPdRu multi-element alloy nanoparticles prepared in this embodiment are shown in Figure 1. The XRD results show that the AuIrPtPdRu multi-element alloy nanoparticles are single-phase alloy nanoparticles, and the single-phase structure is a characteristic structure of multi-element alloys. The crystal structure of the AuIrPtPdRu multi-element alloy nanoparticles is fcc, consistent with the crystal structure of pure Au. Simultaneously, the XRD shows a slight change in lattice parameters (peak shift), which proves that Au, as the host structure, enables the uniform mixing of multiple metal elements, leading to lattice distortion. The XPS results show the valence states of each element: Au(-1), Ir(+3), Pt(0), Pd(0), and Ru(0). It can be observed that the valence states of all elements changed, and Au is at -1, proving that under the catalysis of Au, redox reactions occurred between precursor molecules, and the chemical bonds of all precursor molecules were broken and recombined.
[0061] It should be noted that the embodiments described above are merely preferred embodiments of the present invention. For those skilled in the art, various modifications, improvements, and equivalent substitutions can be made to the present invention without departing from its principles, and such modifications, improvements, and equivalent substitutions are also considered to fall within the protection scope of the claims of the present invention.
Claims
1. A general method for preparing multi-element alloy nanoparticles, characterized in that, Includes the following steps: S1. A precursor material solution is prepared by preparing a precursor of gold as the main catalyst, at least one reducing agent metal precursor, and one or more metal precursors that can be incorporated by electrostatic interaction. The precursor of the main catalyst gold is AuCl3; The reducing agent metal precursor includes VCl3, CrCl3, MnCl2, MoCl5, RuCl3, RhCl3, PdCl2, ReCl3 or IrCl4; The metal precursors that can be incorporated through electrostatic interaction include ScCl3, FeCl3, CoCl2, NiCl2, CuCl2, ZnCl2, YCl3, ZrCl4, NbCl5, TaCl5, WCl6, or PtCl4. S2. Mix the precursor material solutions obtained in step S1 evenly to obtain a mixture; S3. Let the mixture obtained in step S2 stand for 3 to 24 hours until colloidal particles or precipitates are observed in the mixture. S4 The solution obtained in step S3 after standing was washed with hot water and hot anhydrous ethanol by centrifugation to obtain multi-element alloy nanoparticles.
2. The general method for preparing multi-element alloy nanoparticles according to claim 1, characterized in that, In step S1, the concentration of each precursor material solution is arbitrary.
3. The general method for preparing multi-element alloy nanoparticles according to claim 1, characterized in that, In step S4, the solution obtained in step S3 after standing is washed at least three times with hot water and hot anhydrous ethanol.