Supported aluminum-based alloy / intermetallic compound and method of making same

Abstract

This invention relates to a supported aluminum-based alloy / intermetallic compound and its preparation method. The invention ingeniously utilizes the low reduction potential of aluminum to reduce and load a metal salt onto the aluminum surface. Newly generated target metal atoms immediately nucleate and grow on the aluminum surface, interacting with aluminum through solid-phase diffusion. Supported aluminum-based alloys and intermetallic compounds are synthesized at different heat treatment temperatures. Simultaneously, leveraging the high chemical reactivity of aluminum, a series of novel nano-aluminum-based alloys / intermetallic compounds are synthesized under mild conditions through metal-support reactive interactions. Compared to traditional preparation methods, this invention can achieve highly dispersed, high specific surface area, and size-tunable nanoscale supported aluminum-based alloys / intermetallic compounds at lower temperatures, solving the problems of excessively high temperatures (above 1200℃), large material sizes, and inability to synthesize supported aluminum-based alloys / intermetallic compounds required by traditional methods.

Description

Technical Field

[0001] This invention belongs to the field of new material preparation and relates to a supported aluminum-based alloy / intermetallic compound and its preparation method. Background Technology

[0002] Aluminum-based alloys / intermetallic compounds are solid metallic materials formed by aluminum bonded to one or more other metallic elements through metallic bonds. Structurally, aluminum-based alloys typically refer to solid solutions with aluminum as the matrix and other metallic elements dissolved within or existing as a second phase; their structure is relatively loose and their composition is tunable. Aluminum-based intermetallic compounds, on the other hand, refer to compounds formed by aluminum bonded to other metal atoms in specific stoichiometric ratios, exhibiting long-range ordered crystal structures. These compounds typically display high melting points, high strength, and high stability. In recent years, these aluminum-based materials, especially highly ordered intermetallic compounds, have gradually shifted from structural materials to functional materials, demonstrating enormous application potential in the field of heterogeneous catalysis. This long-range ordered crystal structure ensures the uniformity of active sites, facilitating the study of structure-activity relationships and providing theoretical guidance for the design and synthesis of novel catalytic materials.

[0003] Despite the promising applications of aluminum-based alloy / intermetallic compound catalysts, their controllable synthesis, particularly the achievement of highly dispersed, size-tunable, and structurally well-defined nanostructures, as well as supported aluminum-based alloys / intermetallic compounds, remains a significant challenge. Currently, the mainstream synthesis methods mainly include wet chemical reduction and high-temperature melting. Wet chemical reduction is only suitable for some low-boiling-point alloy systems and requires the addition of extra surfactants and reducing agents, making it complex and difficult to prepare on a large scale. Furthermore, alloys prepared by wet chemical methods are usually solid solutions, making it impossible to prepare intermetallic compounds with a predetermined atomic stoichiometry. High-temperature melting is a traditional method for preparing intermetallic compounds. However, this method requires extremely high temperatures (1200 ℃~2000 ℃), consumes a huge amount of energy, and yields mostly dense bulk materials with extremely low specific surface areas, failing to provide sufficient active sites for catalytic reactions. Complex post-processing is required to expose active sites, making the process cumbersome and difficult to control.

[0004] In recent years, mechanical alloying has also been used to prepare intermetallic compounds. However, this method still yields bulk materials with low specific surface areas, limiting the number of active sites and restricting its application in catalysis. Furthermore, all Al in this method participates in alloying, making it impossible to prepare supported intermetallic compounds. Therefore, there is an urgent need to develop a universal synthetic strategy for nanoscale supported aluminum-based alloys / intermetallic compounds that is simple to synthesize, low in cost, low in energy consumption, and capable of achieving high dispersibility, high specific surface area, and tunable size at relatively low temperatures. Summary of the Invention

[0005] The purpose of this invention is to address the problems existing in the prior art by providing a supported aluminum-based alloy / intermetallic compound and its preparation method. This invention ingeniously utilizes the low reduction potential of aluminum to reduce and load a metal salt onto the aluminum surface. The newly generated target metal atoms immediately nucleate and grow on the aluminum surface, interacting with aluminum through solid-phase diffusion to construct aluminum-based alloys / intermetallic compounds from the bottom up. Simultaneously, leveraging the high chemical reactivity of aluminum, a series of novel nano-aluminum-based alloys / intermetallic compounds are synthesized under mild conditions (below 1000℃) through metal-support reactive interactions. This solves the problems of traditional methods requiring excessively high temperatures (above 1200℃), large material sizes, and the inability to synthesize supported aluminum-based alloys / intermetallic compounds.

[0006] The objective of this invention can be achieved through the following methods: In a first aspect, the present invention provides a method for preparing a supported aluminum-based alloy / intermetallic compound, comprising the following steps: S1. Mix aluminum with metallic M salt and grind or ball mill to obtain surface-modified aluminum material; Alternatively, aluminum and metallic M salt can be dispersed in a solvent, stirred to react, and then centrifuged or the solvent can be dried to obtain surface-modified aluminum materials. The metal M salt is selected from one or more of chloride salts, nitrate salts, sulfate salts, acetylacetone salts, carbonyl salts, and acetate salts; S2. The surface-modified aluminum material is heat-treated to obtain a supported aluminum-based alloy / intermetallic compound. Specifically, when the metal M salt is a chloride, nitrate, sulfate, or acetate salt, an aluminum-based alloy with AlM supported on an aluminum support is prepared at a heat treatment temperature of 300-450℃; an intermetallic compound with AlM supported on an aluminum support is prepared at a heat treatment temperature of 500-1000℃. When the metal M salt is an acetylacetone salt or carbonyl salt, an aluminum-based alloy with AlM supported on an aluminum support is prepared at a heat treatment temperature of 300-550℃; an intermetallic compound with AlM supported on an aluminum support is prepared at a heat treatment temperature of 600-1000℃.

[0007] In this invention, the aluminum-based alloy / intermetallic compound consists of two parts: one part is aluminum particles that have not participated in alloying, which serve as a carrier; the other part is Al particles that participate in alloying, which are formed from Al and metallic M. x M y Alloy, thus forming Al x M y Aluminum-based alloys / intermetallic compounds loaded on an Al support.

[0008] As one embodiment of the present invention, in step S1, the metal M salt may also be selected from other organic salts.

[0009] As one embodiment of the present invention, in step S1, the metal M includes one or more of Sc, Ta, Mn, Fe, Co, Ni, Cu, Zr, Nb, Mo, Ru, Rh, Pd, Ag, W, Pt, and Au.

[0010] In one embodiment of the present invention, in step S1, the time for mixing and grinding or ball milling is 5 to 300 minutes, preferably 30 to 120 minutes.

[0011] As one embodiment of the present invention, in step S1, the stirring reaction time is greater than 0 h, preferably 0.5 to 24 h, and more preferably 10 to 20 h.

[0012] As one embodiment of the present invention, in step S1, the solvent is an aprotic solvent, including one or more of toluene, hexane, cyclohexane, methylcyclohexane, 1,4-dioxane, tetrahydrofuran, and dichloromethane.

[0013] In one embodiment of the present invention, in step S2, the mass fraction of metal M in the supported aluminum-based alloy / intermetallic compound is less than 99%.

[0014] In one embodiment of the present invention, in step S2, the heat treatment time is 0.5-24 h, and the heating rate is 0.5-10 ℃ min. -1 .

[0015] In one embodiment of the present invention, in step S2, the heat treatment is carried out in a non-oxidizing atmosphere, including one or more of argon, nitrogen, and hydrogen, preferably hydrogen. The heat treatment can be carried out under negative pressure, atmospheric pressure, or high pressure conditions. The purpose of the heat treatment is to promote Al diffusion and alloying.

[0016] In one embodiment of the present invention, in step S2, the obtained aluminum-based alloy is Al. x M y M includes one or more of Sc, Mn, Fe, Co, Ni, Ta, Cu, Zr, Nb, Mo, Ru, Rh, Pd, Ag, W, Pt, and Au; the resulting aluminum-based intermetallic compound materials include Al3Sc, Al3Ta, Al6Mn, and Al 13 Fe4, Al9Co2, Al3Ni, Al2Cu, Al3Zr, Al3Nb, Al 12 Mo, Al6Ru, Al 13 Rh4, Al6Pd, AlAg2, Al 12One of W, Al2Pt, and Al2Au.

[0017] In one embodiment of the present invention, in step S2, the particle size of the supported aluminum-based alloy / intermetallic compound is 5~200 nm; when the metal content is below 10%, the particle size of the obtained aluminum-based alloy / intermetallic compound is 5~20 nm; when the metal content is 10-30%, the particle size of the obtained aluminum-based alloy / intermetallic compound is 10~100 nm; when the metal content is above 30%, the particle size of the obtained aluminum-based alloy / intermetallic compound is 100-200 nm.

[0018] Secondly, the present invention provides a supported aluminum-based alloy / intermetallic compound obtained by the preparation method described above. This supported aluminum-based alloy / intermetallic compound can be used in catalytic hydrogenation, ammonia synthesis / ammonia decomposition, catalytic oxidation, dehydrogenation reactions, carbon dioxide reduction, or energy storage or conversion.

[0019] Compared with the prior art, the present invention has the following beneficial effects: 1. This invention ingeniously utilizes the low reduction potential of aluminum to reduce and load metal salts onto the aluminum surface. The newly generated target metal atoms immediately nucleate and grow on the aluminum surface, interacting with aluminum through solid-phase diffusion. At different heat treatment temperatures, supported aluminum-based alloys or intermetallic compounds are synthesized respectively. At the same time, by utilizing the high chemical reactivity of aluminum, a series of novel nano-aluminum-based alloys / intermetallic compounds are synthesized under mild conditions through metal-support reactive interactions.

[0020] 2. Compared with the traditional high-temperature smelting method, the present invention can achieve highly dispersed, high specific surface area, and size-adjustable nanoscale supported aluminum-based alloys / intermetallic compounds at a lower temperature (below 1000℃), which solves the problems of the traditional method requiring too high a temperature (above 1200℃), too high energy consumption, and the products obtained are mostly dense bulk with extremely low specific surface area.

[0021] 3. Compared with the traditional mechanical alloying method, this invention cleverly utilizes the low reduction potential of aluminum to reduce the metal salt and load it onto the aluminum surface by mixing the carrier aluminum with the metal salt, rather than directly mixing the carrier aluminum with the metal. The metal salt interacts with the aluminum through solid-phase diffusion, which enables the successful synthesis of nanoscale supported aluminum-based alloys / intermetallic compounds with high specific surface area. This solves the problems of large size and inability to synthesize supported aluminum-based alloys / intermetallic compounds in the traditional mechanical alloying method, making it suitable for large-scale preparation. Attached Figure Description

[0022] Other features, objects, and advantages of the present invention will become more apparent from the following detailed description of non-limiting embodiments with reference to the accompanying drawings: Figure 1 This is the XRD pattern of the Al2Au intermetallic compound prepared in Example 1 loaded on Al; Figure 2 This is the XRD pattern of the Al2Cu intermetallic compound prepared in Example 2 loaded on Al; Figure 3 This is the XRD pattern of the Al2Pt intermetallic compound prepared in Example 3 loaded on Al; Figure 4 This is the XRD pattern of the Al3Ni intermetallic compound prepared in Example 4 loaded on Al; Figure 5 This is the XRD pattern of the Al3Nb intermetallic compound prepared in Example 5 loaded on Al; Figure 6 This is the XRD pattern of the Al3Sc intermetallic compound prepared in Example 6 loaded on Al; Figure 7 This is the XRD pattern of the Al3Ta intermetallic compound prepared in Example 7 loaded on Al; Figure 8 This is the XRD pattern of the Al3Zr intermetallic compound prepared in Example 8 loaded on Al; Figure 9 This is the XRD pattern of the Al6Mn intermetallic compound prepared in Example 9 loaded on Al; Figure 10 This is the XRD pattern of the Al6Pd intermetallic compound prepared in Example 10 loaded on Al; Figure 11 This is the XRD pattern of the Al6Ru intermetallic compound prepared in Example 11 loaded on Al; Figure 12 This is the XRD pattern of the Al9Co2 intermetallic compound prepared in Example 12 loaded on Al; Figure 13 It is the Al prepared in Example 13 12 XRD pattern of W intermetallic compounds loaded on Al; Figure 14 It is the Al prepared in Example 14 12 XRD pattern of Mo intermetallic compounds loaded on Al; Figure 15 This is the XRD pattern of the AlAg2 intermetallic compound prepared in Example 15 loaded on Al; Figure 16 It is the Al prepared in Example 16 13 XRD pattern of Rh4 intermetallic compound loaded on Al; Figure 17 It is the Al prepared in Example 1713 XRD pattern of Fe4 intermetallic compounds loaded on Al; Figure 18 It is the Al prepared in Example 18 x Ni y XRD pattern of alloy loading on Al; Figure 19 It is the Al prepared in Example 19 x Fe y XRD pattern of alloy loading on Al; Figure 20 It is the Al prepared in Example 19 x Fe y STEM image of alloy loading on Al.

[0023] Figure 21 This is a schematic diagram illustrating the synthesis principle of the supported aluminum-based alloy / intermetallic compound of the present invention. Detailed Implementation

[0024] The present invention will now be described in detail with reference to the accompanying drawings and specific embodiments. The following examples are implemented under the premise of the technical solution of the present invention, providing detailed implementation methods and specific operating procedures, which will help those skilled in the art to further understand the present invention. It should be noted that the scope of protection of the present invention is not limited to the following embodiments; any adjustments and improvements made under the concept of the present invention are all within the scope of protection of the present invention.

[0025] Example 1 Preparation of Al2Au-supported Al materials Weigh 19 mg of gold acetate and 90 mg of Al, grind for 1 h, seal in a tantalum crucible, then place in a tube furnace, introduce a 5% H2 / Ar mixed gas, and heat at 5 °C for 1 min. -1 The heating rate was adjusted, and the material was calcined at 550 °C for 12 h to obtain an intermetallic compound material of Al2Au supported on aluminum.

[0026] Example 2 Preparation of Al₂Cu-supported Al materials Weigh 21 mg of copper chloride and 90 mg of Al, grind them for 1 h, seal them in a tantalum crucible, then place them in a tube furnace, introduce a 5% H2 / Ar mixed gas, and heat at 5 °C for 1 min. -1 The heating rate was adjusted, and the material was calcined at 550 °C for 12 h to obtain an intermetallic compound material of Al2Cu supported on aluminum.

[0027] Example 3 Preparation of Al2Pt-supported Al materials Weigh 14 mg of platinum dichloride and 90 mg of Al, grind them for 1 h, seal them in a tantalum crucible, then place them in a tube furnace, introduce a 5% H2 / Ar mixed gas, and heat at 5 °C for 1 min. -1 The heating rate was adjusted, and the material was calcined at 550 °C for 12 h to obtain an intermetallic compound material of Al2Pt supported on aluminum.

[0028] Example 4 Preparation of Al3Ni-supported Al materials Weigh 22 mg of anhydrous nickel chloride and 90 mg of Al, grind for 1 h, seal in a tantalum crucible, then place in a tube furnace, introduce a 5% H2 / Ar mixed gas, and heat at 5 °C for 1 min. -1 The heating rate was adjusted, and the material was calcined at 550 °C for 12 h to obtain an intermetallic compound material of Al3Ni supported on aluminum.

[0029] Example 5 Preparation of Al3Nb-supported Al materials Weigh 29 mg of anhydrous niobium pentachloride and 90 mg of Al, grind for 1 h, seal in a tantalum crucible, then place in a tube furnace, introduce a 5% H2 / Ar mixed gas, and heat at 5 °C for 1 min. -1 By adjusting the heating rate, calcination was carried out at 550 °C for 12 h to obtain an intermetallic compound material of Al3Nb supported on aluminum.

[0030] Example 6 Preparation of Al3Sc-supported Al materials Weigh 34 mg of anhydrous scandium trichloride and 90 mg of Al, grind them for 1 h, seal them in a tantalum crucible, then place them in a tube furnace, introduce a 5% H2 / Ar mixed gas, and heat at 5 °C for 1 min. -1 The heating rate was adjusted, and the material was calcined at 550 °C for 12 h to obtain an intermetallic compound material of Al3Sc supported on aluminum.

[0031] Example 7 Preparation of Al3Ta-supported Al materials Weigh 20 mg of tantalum pentachloride and 90 mg of Al, grind them for 1 h, seal them in a tantalum crucible, then place the crucible in a tube furnace, introduce a 5% H2 / Ar mixed gas, and heat at 5 °C for 1 min. -1 The heating rate was adjusted, and the material was calcined at 550 °C for 12 h to obtain an intermetallic compound material of Al3Ta supported on aluminum.

[0032] Example 8 Preparation of Al3Zr-supported Al materials Weigh 26 mg of zirconium tetrachloride and 90 mg of Al, grind them for 1 h, seal them in a tantalum crucible, then place them in a tube furnace, introduce a 5% H2 / Ar mixed gas, and heat at 5 °C for 1 min. -1 The heating rate was adjusted, and the material was calcined at 550 °C for 12 h to obtain an intermetallic compound material of Al3Zr supported on aluminum.

[0033] Example 9 Preparation of Al6Mn-supported Al materials Weigh 23 mg of anhydrous manganese dichloride and 90 mg of Al, grind for 1 h, seal in a tantalum crucible, then place in a tube furnace, introduce a 5% H2 / Ar mixed gas, and heat at 5 °C for 1 min. -1 By adjusting the heating rate, calcination was carried out at 550 °C for 12 h to obtain an intermetallic compound material of Al6Mn supported on aluminum.

[0034] Example 10 Preparation of Al6Pd-supported Al materials Weigh 17 mg palladium dichloride and 90 mg Al, grind them for 1 h, seal them in a tantalum crucible, then place them in a tube furnace, introduce a 5% H2 / Ar mixed gas, and heat at 5 °C for 1 min. -1 By adjusting the heating rate, calcination was carried out at 550 °C for 12 h to obtain an intermetallic compound material with Al6Pd supported on aluminum.

[0035] Example 11 Preparation of Al6Ru-supported Al materials Weigh 26 mg of ruthenium trichloride trihydrate and 90 mg of Al, grind them for 1 h, seal them in a tantalum crucible, then place them in a tube furnace, introduce a 5% H2 / Ar mixed gas, and heat at 5 °C for 1 min. -1 The heating rate was adjusted, and the material was calcined at 550 °C for 12 h to obtain an intermetallic compound material of Al6Ru supported on aluminum.

[0036] Example 12 Preparation of Al9Co2-loaded Al materials Weigh 22 mg of cobalt dichloride and 90 mg of Al, grind them for 1 h, seal them in a tantalum crucible, then place them in a tube furnace, introduce a 5% H2 / Ar mixed gas, and heat at 5 °C for 1 min. -1 The heating rate was adjusted, and the material was calcined at 550 °C for 12 h to obtain an intermetallic compound material of Al9Co2 supported on aluminum.

[0037] Example 13 Al 12 Preparation of materials loaded on Al Weigh 20 mg of tungsten pentachloride and 90 mg of Al, grind them for 1 h, seal them in a tantalum crucible, then place them in a tube furnace, introduce a 5% H2 / Ar mixed gas, and heat at 5 °C for 1 min. -1 The heating rate was adjusted, and Al was calcined at 550 °C for 12 h to obtain Al. 12 W is an intermetallic compound material loaded on aluminum.

[0038] Example 14 Al 12 Preparation of Mo-supported Al materials Weigh 34 mg of molybdenum acetylacetonate and 90 mg of Al, grind for 1 h, seal in a tantalum crucible, then place in a tube furnace, introduce a 5% H2 / Ar mixed gas, and heat at 5 °C for 1 min. -1 The heating rate was adjusted, and Al was obtained by calcination at 600 °C for 12 h. 12 Mo-supported intermetallic compound materials on aluminum.

[0039] Example 15 Preparation of AlAg2-loaded Al materials Weigh 13 mg of silver chloride and 90 mg of Al, grind them for 1 h, seal them in a tantalum crucible, then place them in a tube furnace, and introduce a 5% H2 / Ar mixed gas at 5 °C for 1 min. -1 The heating rate was adjusted, and the material was calcined at 550 °C for 12 h to obtain an intermetallic compound material of AlAg2 supported on aluminum.

[0040] Example 16 Al 13 Preparation of Rh4-loaded Al materials Weigh 20 mg of anhydrous rhodium chloride and 90 mg of Al, grind them for 1 h, seal them in a tantalum crucible, then place them in a tube furnace, introduce a 5% H2 / Ar mixed gas, and heat at 5 °C for 1 min. -1 The heating rate was adjusted, and Al was calcined at 550 °C for 12 h to obtain Al. 13 Rh4 is an intermetallic compound material supported on aluminum.

[0041] Example 17 Al 13 Preparation of Fe4-supported Al materials Weigh 29 mg of anhydrous ferric chloride and 90 mg of Al, grind them for 1 h, seal them in a tantalum crucible, then place them in a tube furnace, introduce a 5% H2 / Ar mixed gas, and heat at 5 °C for 1 min. -1 The heating rate was adjusted, and Al was calcined at 550 °C for 12 h to obtain Al. 13 Fe4-supported intermetallic compound material on aluminum.

[0042] Example 18 Preparation of AlNi alloy supported on Al Weigh 22 mg of nickel acetylacetone and 90 mg of Al, grind for 1 h, seal in a tantalum crucible, then place in a tube furnace, introduce a 5% H2 / Ar mixed gas, and heat at 5 °C for 1 min. -1 The heating rate was adjusted, and the material was calcined at 450 °C for 12 h to obtain an aluminum-based alloy material with AlNi supported on aluminum.

[0043] Example 19 Preparation of AlFe alloys supported on Al Weigh 32 mg of carbonyl iron and 90 mg of Al, grind them for 1 h, seal them in a tantalum crucible, then place them in a tube furnace, introduce a 5% H2 / Ar mixed gas, and heat at 5 °C for 1 min. -1 The heating rate was adjusted, and the aluminum-based alloy material with AlFe supported on aluminum was obtained by calcination at 450 °C for 12 h.

[0044] Characterization of experimental results The Al2Au-loaded Al sample prepared in Example 1 was characterized by XRD. Figure 1 As can be seen, apart from the characteristic peaks of metallic aluminum, all other peaks on the XRD spectrum are characteristic peaks of Al2Au intermetallic compounds, with no impurity peaks. This indicates that after calcination, metallic aluminum reacts with transition metal salts to form Al2Au intermetallic compounds.

[0045] The Al₂Cu-loaded Al sample prepared in Example 2 was characterized by XRD. Figure 2 As can be seen, apart from the characteristic peaks of metallic aluminum, all other peaks in the XRD spectrum are characteristic peaks of Al2Cu intermetallic compounds, with no impurity peaks. This indicates that after calcination, metallic aluminum reacts with transition metal salts to form Al2Cu intermetallic compounds.

[0046] The Al2Pt-loaded Al sample prepared in Example 3 was characterized by XRD. Figure 3 As can be seen, apart from the characteristic peaks of metallic aluminum, all other peaks in the XRD spectrum are characteristic peaks of Al2Pt intermetallic compounds, with no impurity peaks. This indicates that after calcination, metallic aluminum reacts with transition metal salts to form Al2Pt intermetallic compounds.

[0047] The Al3Ni-loaded Al sample prepared in Example 4 was characterized by XRD. Figure 4As can be seen, apart from the characteristic peaks of metallic aluminum, all other peaks in the XRD spectrum are characteristic peaks of Al3Ni intermetallic compounds, with no impurity peaks. This indicates that after calcination, metallic aluminum reacts with transition metal salts to form Al3Ni intermetallic compounds.

[0048] The Al3Nb-loaded Al sample prepared in Example 5 was characterized by XRD. Figure 5 As can be seen, apart from the characteristic peaks of metallic aluminum, all other peaks in the XRD spectrum are characteristic peaks of Al3Nb intermetallic compounds, with no impurity peaks. This indicates that after calcination, metallic aluminum reacts with transition metal salts to form Al3Nb intermetallic compounds.

[0049] The Al3Sc-loaded Al sample prepared in Example 6 was characterized by XRD. Figure 6 As can be seen, apart from the characteristic peaks of metallic aluminum, all other peaks in the XRD spectrum are characteristic peaks of Al3Sc intermetallic compounds, with no impurity peaks. This indicates that after calcination, metallic aluminum reacts with transition metal salts to form Al3Sc intermetallic compounds.

[0050] The Al3Ta-loaded Al sample prepared in Example 7 was characterized by XRD. Figure 7 As can be seen, apart from the characteristic peaks of metallic aluminum, all other peaks in the XRD spectrum are characteristic peaks of Al3Ta intermetallic compounds, with no impurity peaks. This indicates that after calcination, metallic aluminum reacts with transition metal salts to form Al3Ta intermetallic compounds.

[0051] The Al3Zr-loaded Al sample prepared in Example 8 was characterized by XRD. Figure 8 As can be seen, apart from the characteristic peaks of metallic aluminum, all other peaks in the XRD spectrum are characteristic peaks of Al3Zr intermetallic compounds, with no impurity peaks. This indicates that after calcination, metallic aluminum reacts with transition metal salts to form Al3Zr intermetallic compounds.

[0052] The Al6Mn-loaded Al sample prepared in Example 9 was characterized by XRD. Figure 9 As can be seen, apart from the characteristic peaks of metallic aluminum, all other peaks in the XRD spectrum are characteristic peaks of Al6Mn intermetallic compounds, with no impurity peaks. This indicates that after calcination, metallic aluminum reacts with transition metal salts to form Al6Mn intermetallic compounds.

[0053] The Al6Pd-loaded Al sample prepared in Example 10 was characterized by XRD. Figure 10As can be seen, apart from the characteristic peaks of metallic aluminum, all other peaks in the XRD spectrum are characteristic peaks of Al6Pd intermetallic compounds, with no impurity peaks. This indicates that after calcination, metallic aluminum reacts with transition metal salts to form Al6Pd intermetallic compounds.

[0054] The Al6Ru-loaded Al sample prepared in Example 11 was characterized by XRD. Figure 11 As can be seen, apart from the characteristic peaks of metallic aluminum, all other peaks in the XRD spectrum are characteristic peaks of Al6Ru intermetallic compounds, with no impurity peaks. This indicates that after calcination, metallic aluminum reacts with transition metal salts to form Al6Ru intermetallic compounds.

[0055] The Al9Co2-loaded Al sample prepared in Example 12 was characterized by XRD. Figure 12 As can be seen, apart from the characteristic peaks of metallic aluminum, all other peaks on the XRD spectrum are characteristic peaks of Al9Co2 intermetallic compounds, with no impurity peaks. This indicates that after calcination, metallic aluminum reacts with transition metal salts to form Al9Co2 intermetallic compounds.

[0056] The Al prepared in Example 13 12 The sample loaded with W on Al was characterized by XRD. Figure 13 As can be seen, apart from the characteristic peaks of metallic aluminum, all other peaks in the XRD spectrum are Al. 12 The presence of characteristic peaks from intermetallic compounds, along with the absence of any impurity peaks, indicates that Al was formed after calcination following a reaction between metallic aluminum and transition metal salts. 12 W intermetallic compounds.

[0057] The Al prepared in Example 14 12 The Mo-loaded Al sample was characterized by XRD. Figure 14 As can be seen, apart from the characteristic peaks of metallic aluminum, all other peaks in the XRD spectrum are Al. 12 The presence of characteristic peaks from Mo intermetallic compounds, along with the absence of any impurity peaks, indicates that Al was formed after calcination following a reaction between metallic aluminum and transition metal salts. 12 Mo intermetallic compounds.

[0058] The AlAg2-loaded Al sample prepared in Example 15 was characterized by XRD. Figure 15 As can be seen, apart from the characteristic peaks of metallic aluminum, all other peaks in the XRD spectrum are characteristic peaks of AlAg2 intermetallic compounds, with no impurity peaks. This indicates that after calcination, metallic aluminum reacts with transition metal salts to form AlAg2 intermetallic compounds.

[0059] The Al prepared in Example 16 13The Rh4-loaded Al sample was characterized by XRD. Figure 16 As can be seen, apart from the characteristic peaks of metallic aluminum, all other peaks in the XRD spectrum are Al. 13 The presence of characteristic peaks from Rh4 intermetallic compounds, along with the absence of any impurity peaks, indicates that Al was formed after calcination following a reaction between metallic aluminum and transition metal salts. 13 Rh4 intermetallic compounds.

[0060] The Al prepared in Example 17 13 The Fe4-loaded Al sample was characterized by XRD. Figure 17 As can be seen from the XRD pattern, apart from the characteristic peaks of metallic aluminum, all other peaks are characteristic of Al₂Au intermetallic compounds, with no impurity peaks. This indicates that after calcination, metallic aluminum reacts with transition metal salts to form Al₂Au. 13 Fe4 intermetallic compounds.

[0061] The AlNi alloy sample prepared in Example 18 and loaded onto Al was characterized by XRD. Figure 18 As can be seen, apart from the characteristic peaks of metallic aluminum, no peaks of Al3Ni intermetallic compounds appeared on the XRD spectrum. Instead, diffraction peaks of elemental Ni shifted to a lower angle appeared. This indicates that at lower temperatures, AlNi can form a disordered solid solution, i.e., an aluminum-based alloy material with AlNi supported on aluminum, without forming intermetallic compounds.

[0062] The AlFe alloy sample prepared in Example 19 and loaded onto Al was characterized by XRD. Figure 19 It can be seen that, apart from the characteristic peaks of metallic aluminum, no Al peaks were observed in the XRD spectrum. 13 Instead of the Fe4 intermetallic compound peak, diffraction peaks of elemental Fe shifted to lower angles appeared. This indicates that at lower temperatures, AlFe can form a disordered solid solution, i.e., an aluminum-based alloy material with AlFe supported on aluminum, without forming intermetallic compounds. This can be seen from transmission electron microscopy, as... Figure 20 The size of the AlFe alloy loaded on the Al substrate is about 9~14 nm, which proves the applicability of the method of the present invention in the preparation of nanoalloy materials.

[0063] This invention uses aluminum as a carrier material and leverages the high reactivity of aluminum through a galvanocoupler substitution method to synthesize a series of nanoscale supported aluminum-based alloys / intermetallic compounds via reactions with other transition metals or metal salts, thus broadening the material system of intermetallic compounds. The synthesis method is applicable to a range of metals with reduction potentials higher than aluminum, demonstrating universality in its synthetic strategy. The synthesis principle is as follows: Figure 21 As shown, the preparation method of the present invention is simple and efficient, produces particles with uniform size, and can be used for large-scale preparation.

[0064] The specific embodiments of the present invention have been described above. It should be understood that the present invention is not limited to the specific embodiments described above, and those skilled in the art can make various modifications or variations within the scope of the claims, which do not affect the essence of the present invention.

Claims

1. A method for preparing a supported aluminum-based alloy / intermetallic compound, characterized in that, Includes the following steps: S1. Mix aluminum with metallic M salt and grind or ball mill to obtain surface-modified aluminum material; Alternatively, aluminum and metallic M salt can be dispersed in a solvent, stirred to react, and then centrifuged or the solvent can be dried to obtain surface-modified aluminum materials. The metal M salt is selected from one or more of chloride salts, nitrate salts, sulfate salts, acetylacetone salts, carbonyl salts, and acetate salts; S2. The surface-modified aluminum material is heat-treated to obtain a supported aluminum-based alloy / intermetallic compound. Specifically, when the metal M salt is a chloride, nitrate, sulfate, or acetate salt, an aluminum-based alloy with AlM supported on an aluminum support is prepared at a heat treatment temperature of 300–450 °C; an intermetallic compound with AlM supported on an aluminum support is prepared at a heat treatment temperature of 500–1000 °C. When the metal M salt is an acetylacetone salt or carbonyl salt, an aluminum-based alloy with AlM supported on an aluminum support is prepared at a heat treatment temperature of 300–550 °C; an intermetallic compound with AlM supported on an aluminum support is prepared at a heat treatment temperature of 600–1000 °C.

2. The preparation method according to claim 1, characterized in that, In step S1, the metal M includes one or more of Sc, Ta, Mn, Fe, Co, Ni, Cu, Zr, Nb, Mo, Ru, Rh, Pd, Ag, W, Pt, and Au.

3. The preparation method according to claim 1, characterized in that, In step S1, the time for mixing and grinding or ball milling is 5 to 300 minutes.

4. The preparation method according to claim 1, characterized in that, In step S1, the stirring reaction time is 0.5 to 24 hours.

5. The preparation method according to claim 1, characterized in that, In step S1, the solvent is an aprotic solvent, including one or more of toluene, hexane, cyclohexane, methylcyclohexane, 1,4-dioxane, tetrahydrofuran, and dichloromethane.

6. The preparation method according to claim 1, characterized in that, In step S2, the mass fraction of metal M in the supported aluminum-based alloy / intermetallic compound is less than 99%.

7. The preparation method according to claim 1, characterized in that, In step S2, the heat treatment time is 0.5-24 h, and the heating rate is 0.5-10 ℃min. -1 .

8. The preparation method according to claim 1, characterized in that, In step S2, the heat treatment is carried out in a non-oxidizing atmosphere, which includes one or more of argon, nitrogen, hydrogen, etc.

9. The preparation method according to claim 1, characterized in that, In step S2, the particle size of the supported aluminum-based alloy / intermetallic compound is 5~200 nm.

10. A supported aluminum-based alloy / intermetallic compound obtained by the preparation method according to any one of claims 1-9.

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