A copper-based intermetallic compound porous material, a preparation method and application thereof

Abstract

The embodiment of the present application relates to a kind of copper intermetallic compound porous materials and its preparation method and application, wherein, preparation method includes: metal Mg, Zn, Cu, M is mixed, is handled by induction smelting, and MgZnCuM alloy ingot is obtained;MgZnCuM alloy ingot is treated by spinning, and MgZnCuM precursor is obtained;MgZnCuM precursor is placed in gas phase de-alloying system and is treated by first vacuum heat treatment, and copper intermetallic compound porous material MgCuM is obtained;MgCuM has double continuous structure.The preparation method is simple and easy to operate, pore size is adjustable, and pore distribution is uniform, and the preparation process is environment-friendly and pollution-free.

Description

Technical Field

[0001] This invention relates to the field of materials technology, and in particular to a copper-based intermetallic compound porous material, its preparation method, and its application. Background Technology

[0002] Currently, porous metallic materials have attracted much attention and are widely used in fields such as batteries, aerospace, aviation, energy storage, medicine, and chemical engineering due to their ultra-large specific surface area and excellent electrical / thermal conductivity. The main methods for preparing porous metallic materials include electrodeposition, chemical / electrochemical dealloying, solid-state sintering, liquid solidification, wet spraying, and liquid metal dealloying. These methods produce porous materials with varying porosity and pore size characteristics, making them suitable for different applications.

[0003] Chemical / electrochemical dealloying and liquid metal dealloying are commonly used to prepare porous metals with bicontinuous structures. Chemical / electrochemical dealloying utilizes the difference in standard electrode potentials of elements or the selectivity of metals in the etching solution to complete the dealloying process, thus forming a porous structure. Chemical / electrochemical dealloying is particularly effective for manufacturing noble metals and easily passivated porous materials, such as metals Pt, Pd, Au, and Ag. Liquid metal dealloying, on the other hand, utilizes the compatibility differences between alloy components and molten metal to prepare nanoporous metals. While it has a higher dealloying temperature, it is limited by the choice of elements, resulting in a limited variety of materials that can be prepared. Furthermore, the molten metal from dealloying is difficult to recover and easily remains within the pores, clogging the channels. In short, these methods generally result in chemical corrosion, leading to unavoidable environmental pollution problems.

[0004] Intermetallic compounds possess excellent electrical conductivity. Their metal atoms are bonded together through covalent and metallic bonds, forming an electron cloud, thus exhibiting superior conductivity and finding wide applications in electronics, power, communications, and other fields. Furthermore, the strong metallic bonds in intermetallic compounds typically result in high melting points and excellent thermal stability. The metal-metal bonds also contribute to their high strength and toughness, making them suitable for manufacturing high-quality structural materials, parts, and mechanical components. Intermetallic compounds exhibit good corrosion resistance, demonstrating promising applications in harsh environments such as strong corrosion and corrosion. Some intermetallic compounds also exhibit high chemical reactivity, undergoing rapid redox reactions, which can lead to wide applications in electrocatalysis and sensing.

[0005] However, current methods for preparing porous intermetallic compounds mainly involve compression molding-vacuum sintering, thermal explosion reaction, reactive synthesis, template methods, sol-gel methods, and co-precipitation methods. The products are primarily iron-based, aluminum-based, and nickel-based porous materials. These products lack a bicontinuous porous structure and have relatively large pore sizes, ranging from tens to hundreds of micrometers, significantly reducing the specific surface area of ​​the materials. Furthermore, these methods are not universally applicable for developing other types of porous intermetallic compound materials. Summary of the Invention

[0006] The purpose of this invention is to address the shortcomings of existing technologies by providing a copper-based intermetallic compound porous material, its preparation method, and its applications.

[0007] To achieve the above objectives, in a first aspect, the present invention provides a method for preparing copper-based intermetallic compound porous materials, the method comprising:

[0008] Metals Mg, Zn, Cu, and M are mixed and subjected to induction melting to obtain MgZnCuM alloy ingots;

[0009] The MgZnCuM alloy ingot was subjected to a strip spinning process to obtain the MgZnCuM precursor;

[0010] The MgZnCuM precursor was subjected to a first vacuum heat treatment in a vapor-phase dealloying system to obtain a copper-based intermetallic porous material MgCuM; the MgCuM has a bicontinuous structure.

[0011] Preferably, after obtaining the copper-based intermetallic porous material MgCuM, the method further includes:

[0012] The copper-based intermetallic porous material MgCuM is placed in the vapor-phase dealloying system for a second vacuum heat treatment to obtain copper-based intermetallic porous material CuM; the CuM has a bicontinuous structure.

[0013] Preferably, after obtaining the MgZnCuM precursor, the process further includes:

[0014] The MgZnCuM precursor was subjected to a third vacuum heat treatment in a vapor-phase dealloying system to obtain CuM, a copper-based intermetallic porous material; the CuM has a bicontinuous structure.

[0015] Preferably, the conditions for the induction melting process are: induction current 18A-22A, vacuum degree 1×10⁻⁶. -3 Pa-3×10 -3 Pa;

[0016] The conditions for the belt spinning process are: inert atmosphere, current 22A-26A, vacuum degree 7.5×10⁻⁶.4 Pa -8.5×10 4 Pa, copper roller speed 900r / min-1100r / min, time 20s-30s.

[0017] More preferably, the MgZnCuM alloy ingot is Mg x Zn y (Cu3Al2) z Alloy ingot, wherein 30≤x≤40, 30≤y≤40, 20≤z≤40.

[0018] More preferably, the conditions for the first vacuum heat treatment are: vacuum degree 1×10⁻⁶. -4 Pa-2×10 -4 Pa, heating rate of 9K / min-11K / min, temperature of 693K-773K, time of 3-6 hours.

[0019] More preferably, the MgZnCuM alloy ingot is Mg x Zn y (Cu5Si) z Alloy ingot, wherein 30≤x≤40, 30≤y≤40, 20≤z≤40.

[0020] More preferably, the conditions for the first vacuum heat treatment are: vacuum degree 1×10⁻⁶. -4 Pa-2×10 -4 Pa, heating rate of 9K / min-11K / min, temperature of 733K-873K, time of 2-7 hours.

[0021] In a second aspect, the present invention provides a copper-based intermetallic compound porous material, which is prepared by any of the preparation methods described in the first aspect above.

[0022] Thirdly, the present invention provides an application of the copper-based intermetallic compound porous material described in the second aspect, wherein the copper-based intermetallic compound porous material is used in a glucose sensor or in a catalytic reaction for carbon dioxide reduction.

[0023] The method for preparing copper-based intermetallic porous materials provided in this invention first generates a high-purity alloy ingot through induction melting. Then, the alloy ingot is subjected to a strip spinning process to generate a uniform MgZnCuM precursor. Following this, a vacuum-phase dealloying process is performed, causing the sacrificial elements to continuously sublimate or volatilize. This results in the formation of numerous pores at the sites occupied by the sacrificial element atoms, thus producing a copper-based intermetallic porous material with a bicontinuous structure. This preparation method utilizes the saturated vapor pressure difference between different metal elements, greatly increasing the variety of materials that can be selected. Furthermore, the long dealloying time and high temperature overcome energy barriers to form ordered intermetallic compounds. The removed metal elements can also be recovered. The preparation process is environmentally friendly and pollution-free. In summary, the preparation method of this application is simple and easy to operate, achieving adjustable pore size and uniform pore distribution. Attached Figure Description

[0024] Figure 1 This is a flowchart illustrating the preparation method of copper-based intermetallic compound porous materials provided in this embodiment of the invention.

[0025] Figure 2-a This is one of the SEM images of the MgZnCuAl precursor provided in Embodiment 1 of the present invention during the thermal vacuum treatment process;

[0026] Figure 2-b This is the second SEM image of the MgZnCuAl precursor provided in Embodiment 1 of the present invention during the thermal vacuum treatment process;

[0027] Figure 2-c This is the third SEM image of the MgZnCuAl precursor provided in Embodiment 1 of the present invention during the thermal vacuum treatment process;

[0028] Figure 3 The XRD pattern of the MgZnCuAl precursor provided in Embodiment 1 of the present invention during the thermal vacuum treatment process;

[0029] Figure 4-a This is one of the SEM images of the MgZnCuSi precursor provided in Embodiment 2 of the present invention during the thermal vacuum treatment process;

[0030] Figure 4-b This is the second SEM image of the MgZnCuSi precursor provided in Embodiment 2 of the present invention during the thermal vacuum treatment process;

[0031] Figure 4-c This is the third SEM image of the MgZnCuSi precursor provided in Embodiment 2 of the present invention during the thermal vacuum treatment process;

[0032] Figure 5 The XRD pattern of the MgZnCuSi precursor provided in Embodiment 2 of the present invention during the thermal vacuum treatment process;

[0033] Figure 6-a Here is a surface SEM image of the product prepared in Comparative Example 1 of this invention;

[0034] Figure 6-b This is an internal SEM image of the product prepared in Comparative Example 1 of this invention;

[0035] Figure 7 This is a SEM image of the product prepared in Comparative Example 2 of this invention;

[0036] Figure 8 This is a SEM image of the product prepared in Comparative Example 3 of this invention. Detailed Implementation

[0037] To make the objectives, technical solutions, and advantages of this invention clearer, the invention will be further described in detail below with reference to the accompanying drawings. Obviously, the described embodiments are only a part of the embodiments of this invention, and not all of them. Based on the embodiments of this invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of this invention.

[0038] The technical solution of the present invention will be further described in detail below with reference to the accompanying drawings and embodiments.

[0039] This invention provides a method for preparing copper-based intermetallic compound porous materials, the process of which is as follows: Figure 1 As shown, it includes the following steps:

[0040] Step 110: Mix the metals Mg, Zn, Cu, and M, and then perform induction melting to obtain MgZnCuM alloy ingots;

[0041] Specifically, M can be Al or Si. The MgZnCuM alloy ingot can be Mg. x Zn y (Cu3Al2) z Alloy ingots, wherein 30≤x≤40, 30≤y≤40, 20≤z≤40. MgZnCuM alloy ingots can also be Mg... x Zn y (Cu5Si) z Alloy ingot, wherein 30≤x≤40, 30≤y≤40, 20≤z≤40.

[0042] More specifically, Mg, Zn, Cu, and M are mixed in a preset ratio and placed in a boron nitride crucible. The boron nitride crucible is then placed in an induction melting furnace, which is subsequently evacuated before melting. The preset ratio refers to the atomic proportions of each element in the alloy ingot. The specific conditions for induction melting are: induction current 18A-22A, vacuum degree 1×10⁻⁶. -3 Pa-3×10 -3 Pa, time can be 90s-120s. Preferably, the induction current is 20A, and the vacuum degree is 1×10⁻⁶. -3 Pa, time is 100s-110s.

[0043] Step 120: The MgZnCuM alloy ingot is subjected to a strip spinning process to obtain the MgZnCuM precursor;

[0044] Specifically, the MgZnCuM precursor is a solid solution strip. The conditions for the strip spinning process are: inert atmosphere, current 22A-26A, vacuum degree 7.5×10⁻⁶. 4 Pa -8.5×10 4 Pa, copper roller speed 900r / min-1100r / min, time 20s-30s, preferred current 24A, vacuum degree 8×10 4 Pa, copper roller speed 1000 r / min, time 25 s. The inert atmosphere can be argon and / or nitrogen.

[0045] The purpose of the strip spinning process is to allow the metal to cool rapidly from a high-temperature molten state, resulting in a more uniform composition in the precursor. This uniformity in the MgZnCuM precursor provides a foundation for the uniformity of the subsequent pore structure.

[0046] The quaternary alloy precursor obtained by induction melting has a slow cooling rate, resulting in large grains that are prone to segregation, thus compromising compositional uniformity. Segregated alloy regions are unfavorable for the formation of porous structures during vapor-phase dealloying, or may even be unable to undergo vapor-phase dealloying, making it impossible to prepare ideal porous materials. Strip spinning utilizes induced current to melt the alloy ingot, which is then injected with argon gas onto a high-speed rotating copper roller, causing rapid cooling of the molten metal to form a uniform alloy strip. Rapid cooling refines the grains, and remelting further improves alloy homogeneity.

[0047] As a preferred embodiment, prior to the belt-spinning process, this application also includes:

[0048] The MgZnCuM alloy ingots are polished to remove the surface oxide layer, and then placed in a strip spinning machine. To prevent the surface of the MgZnCuM alloy ingots from being oxidized again, the strip spinning machine is evacuated to a vacuum level of 5 × 10⁻⁶. -4 Pa-8×10-4 Pa, preferably 5×10 -4 Pa. Grinding treatment can include, but is not limited to, any one or more of mechanical grinding, chemical grinding, and mobile grinding.

[0049] Step 130: The MgZnCuM precursor is placed in a vapor-phase dealloying system for the first vacuum heat treatment to obtain the copper-based intermetallic compound porous material MgCuM.

[0050] Specifically, the vapor-phase dealloying system can reach a temperature of 1573 K and the pressure during dealloying can be reduced to 1 × 10⁻⁶. -4 A vacuum tube furnace with a pressure of Pa.

[0051] MgCuM can include MgCuAl or MgCuSi. MgCuAl has a pore size of 100 nm to 300 nm, while MgCuSi has a pore size of 100 nm to 250 nm.

[0052] When MgCuM is MgCuAl, the conditions for the first vacuum heat treatment are: vacuum degree of 1×10⁻⁶. -4 Pa-2×10 - 4 The heating conditions are as follows: Pa, heating rate 9-11 K / min, temperature 693-773 K, time 3-6 hours. Preferred conditions are: vacuum degree 1×10⁻⁶. -4 Pa, heating rate 10 K / min, temperature 693 K, time 4 hours.

[0053] When MgCuM is MgCuSi, the conditions for the first vacuum heat treatment are: vacuum degree of 1×10⁻⁶. -4 Pa-2×10 - 4 The preferred conditions are: Pa, heating rate of 9-11 K / min, temperature of 733-873 K, and time of 2-7 hours. The preferred conditions are: vacuum degree of 1×10⁻⁶. -4 Pa, heating rate 10 K / min, temperature 733 K, time 4 hours.

[0054] It should be noted that during the first heat treatment, the temperature fluctuation should not exceed 1K, which helps to control the time of vapor phase dealloying and will not affect the product.

[0055] In this process, Zn in the MgZnCuM precursor continuously sublimates or volatilizes, while Mg partially sublimates or volatilizes. This results in the formation of numerous pores at sites occupied by Zn atoms and a smaller number of pores at sites occupied by Mg atoms, thereby increasing porosity. The formation of nanoporous structures is usually the result of a competition between the self-organization processes of sacrificial element removal and retention elements in the precursor alloy. The sacrificial element is transported to the surrounding medium at the frontal interface, controlled by the slowest diffusion step and the reorganization reaction process, ultimately forming open pores in a bicontinuous structure.

[0056] MgCuM exhibits a bicontinuous structure. This bicontinuous structure means that the material has three-dimensional interconnected channels, giving it the following advantages:

[0057] First, it offers a high specific surface area, crucial for catalysis and adsorption. Second, the bicontinuous structure maintains porosity while providing good mechanical support; its continuous framework effectively transfers stress. Third, the size, shape, and distribution of pores can be precisely controlled by adjusting preparation conditions, thereby optimizing material performance. Fourth, the bicontinuous structure provides more active sites, improving catalytic efficiency. Fifth, the intermetallic compounds in the bicontinuous structure offer electron conduction pathways, making the material widely applicable in electrocatalysis and electrochemical sensors.

[0058] Following step 130, this application further includes:

[0059] The porous material MgCuM, which is a copper-based intermetallic compound, was placed in a vapor-phase dealloying system for a second vacuum heat treatment to obtain the porous material CuM, which is a copper-based intermetallic compound.

[0060] CuM can include CuAl or CuSi. CuAl has a pore size of 200 nm to 500 nm, while CuSi has a pore size of 200 nm to 380 nm.

[0061] The second vacuum heat treatment is carried out on the basis of the first vacuum heat treatment. During this process, Mg sublimates or volatilizes continuously, resulting in the formation of a large number of pores in the positions occupied by Mg atoms, which can further improve the porosity.

[0062] When CuM is CuAl, the conditions for the second vacuum heat treatment are: vacuum degree 1×10⁻⁶. -4 Pa-2×10 -4 The heating conditions are: Pa, heating rate 10 K / min, temperature 693 K-773 K, time 2-6 hours. Preferred conditions are: vacuum degree 1 × 10⁻⁶. -4 Pa, heating rate 10 K / min, temperature 693 K, time 4 hours.

[0063] When CuM is CuSi, the conditions for the second vacuum heat treatment are: vacuum degree 1×10⁻⁶. -4 Pa-2×10 -4 The heating conditions are: Pa, heating rate 10 K / min, temperature 733 K-873 K, time 4-9 hours. Preferred conditions are: vacuum degree 1×10⁻⁶. -4 Pa, heating rate 10 K / min, temperature 733 K, time 6 hours.

[0064] When only the copper-based intermetallic porous material CuM is needed, step 130 can be omitted. Instead, after step 120, the MgZnCuM precursor can be placed in a vapor-phase dealloying system for a third vacuum heat treatment to obtain the copper-based intermetallic porous material CuM. CuM exhibits a bicontinuous structure.

[0065] When CuM is CuAl, the conditions for the third vacuum heat treatment are: vacuum degree 1×10⁻⁶. -4 Pa-2×10 -4 The heating conditions are: Pa, heating rate 10 K / min, temperature 693 K-773 K, and time 5-12 hours. Preferred conditions are: vacuum degree 1 × 10⁻⁶. -4 Pa, heating rate 10 K / min, temperature 693 K, time 8 hours.

[0066] When CuM is CuSi, the conditions for the third vacuum heat treatment are: vacuum degree 1×10⁻⁶. -4 Pa-2×10 -4 The heating conditions are: Pa, heating rate 10 K / min, temperature 733 K-873 K, time 6-16 hours. Preferred conditions are: vacuum degree 1×10⁻⁶. -4 Pa, heating rate 10 K / min, temperature 733 K, time 12 hours.

[0067] It should be noted that in all vacuum heat treatment conditions of this application, temperature and time are inversely proportional; generally, the higher the temperature, the shorter the time.

[0068] The method for preparing copper-based intermetallic porous materials provided in this invention first generates a high-purity alloy ingot through induction melting. Then, the alloy ingot is subjected to a strip spinning process to generate a uniform MgZnCuM precursor. Following this, a vacuum-phase dealloying process is performed, causing the sacrificial elements to continuously sublimate or volatilize. This results in the formation of numerous pores at the sites occupied by the sacrificial element atoms, thus producing a copper-based intermetallic porous material with a bicontinuous structure. This preparation method utilizes the saturated vapor pressure difference between different metal elements, greatly increasing the variety of materials that can be selected. Furthermore, the long dealloying time and high temperature overcome energy barriers to form ordered intermetallic compounds. The removed metal elements can also be recovered. The preparation process is environmentally friendly and pollution-free. In summary, the preparation method of this application is simple and easy to operate, achieving adjustable pore size and uniform pore distribution.

[0069] The copper-based intermetallic porous material provided by this invention can be applied to glucose sensors or catalytic reactions for carbon dioxide reduction.

[0070] To better understand the technical solution provided by the present invention, the following describes the specific process of preparing copper-based intermetallic compound porous materials using the method provided in the above embodiments of the present invention through several specific examples.

[0071] Example 1

[0072] The first step involves weighing 30g of Mg, Zn, Cu, and Al metal blocks according to the atomic ratio of Mg, Zn, Cu, and Al in the MgZnCuAl alloy ingot of 40:40:12:8, to obtain the alloy precursor.

[0073] The second step involves placing the alloy precursor in a boron nitride crucible, then placing the boron nitride crucible inside an induction melting furnace. The induction melting furnace is then evacuated to a vacuum level of 1×10⁻⁶. -3 A 20A induced current was applied, and induction melting was performed for 100s. After cooling, Mg was obtained. 40 Zn 40 Cu 12 Al8 alloy ingot.

[0074] Third step, take 3g of Mg 40 Zn 40 Cu 12 Al8 alloy ingots are mechanically polished and placed in a belt spinning machine, which is then evacuated to a vacuum level of 5 × 10⁻⁶. -4 Pa, then argon gas is introduced into the belt spinning machine until the vacuum degree is 8×10. 4 Pa, under conditions of 24A current and 1000r / min copper roller speed, was spun for 25s to obtain Mg. 40 Zn 40 Cu 12Al8 precursor.

[0075] Step 4, Mg 40 Zn 40 Cu 12 The Al8 precursor was subjected to a first vacuum heat treatment in a vapor-phase dealloying system to obtain Mg, a copper-based intermetallic porous material with a bicontinuous structure. 30 Cu 42 A l 28 The conditions for the first vacuum heat treatment were a vacuum degree of 1×10⁻⁶. -4 The heating process was carried out at a rate of 10 K / min, a temperature of 693 K, and a time of 4 hours. During this process, Zn completely volatilized along with partial volatilization of Mg, forming a porous structure. It should be noted that the porous material Mg... 30 Cu 42 Al 28 The numbers represent the proportions of various elements, not specific quantities. The examples below are similar and will not be repeated.

[0076] Fifth, a portion of the product from step four is placed in a vapor-phase dealloying system for a second vacuum heat treatment to obtain Cu6Al4, a porous intermetallic compound material with a bicontinuous structure. The conditions for the second vacuum heat treatment are a vacuum degree of 1 × 10⁻⁶. -4 The heating process was carried out at a rate of 10 K / min, a temperature of 693 K, and a time of 4 hours. During this process, Zn and Mg elements completely volatilized to form a porous structure. It should be noted that the numbers in the porous material Cu6Al4 represent the proportions of various elements, not specific quantities. The following examples are similar and will not be described in detail.

[0077] Example 2

[0078] The first step involves weighing 30g of Mg, Zn, Cu and Si metal blocks according to the atomic ratio of Mg, Zn, Cu and Si in the MgZnCuSi alloy ingot of 40:40:16.67:3.33, to obtain the alloy precursor.

[0079] The second step involves placing the alloy precursor in a boron nitride crucible, then placing the boron nitride crucible inside an induction melting furnace. The induction melting furnace is then evacuated to a vacuum level of 1×10⁻⁶. -3 A 20A induced current was applied, and induction melting was performed for 110s. After cooling, Mg was obtained. 40 Zn 40 (Cu5Si) 20 Alloy ingot.

[0080] Third step, take 3g of Mg 40 Zn 40(Cu5Si) 20 The alloy ingots are mechanically polished and placed in a strip spinning machine, which is then evacuated to a vacuum level of 5×10⁻⁶. -4 Pa, then argon gas is introduced into the belt spinning machine until the vacuum degree is 8×10. 4 Pa, under conditions of 24A current and 1000r / min copper roller speed, was spun for 25s to obtain Mg. 40 Zn 40 (Cu5Si) 20 Precursor.

[0081] Step 4, Mg 40 Zn 40 (Cu5Si) 20 The precursor was subjected to a first vacuum heat treatment in a vapor-phase dealloying system to obtain a copper-based intermetallic porous material Mg5Cu with a bicontinuous structure. 10 Si2. The conditions for the first vacuum heat treatment were a vacuum degree of 1×10⁻⁶. -4 Pa, heating rate 10 K / min, temperature 733 K, time 4 hours.

[0082] Fifth, a portion of the product from step four is placed in a vapor-phase dealloying system for a second vacuum heat treatment to obtain Cu5Si, a porous copper-based intermetallic compound with a bicontinuous structure. The conditions for the second vacuum heat treatment are a vacuum degree of 1 × 10⁻⁶. -4 Pa, heating rate 10 K / min, temperature 733 K, time 9 hours.

[0083] Example 3

[0084] The first step involves weighing 30g of Mg, Zn, Cu, and Al metal blocks according to the atomic ratio of Mg, Zn, Cu, and Al in the MgZnCuAl alloy ingot of 40:40:12:8, to obtain the alloy precursor.

[0085] The second step involves placing the alloy precursor in a boron nitride crucible, then placing the boron nitride crucible inside an induction melting furnace. The induction melting furnace is then evacuated to a vacuum level of 2 × 10⁻⁶. -3 A current of 22 A was applied to Pa, and induction melting was carried out for 90 seconds. After cooling, Mg was obtained. 40 Zn 40 Cu 12 Al8 alloy ingot.

[0086] Third step, take 3g of Mg 40 Zn 40 Cu 12Al8 alloy ingots are mechanically polished and placed in a belt spinning machine, which is then evacuated to a vacuum level of 8 × 10⁻⁶. -4 Pa, then argon gas is introduced into the belt spinning machine until the vacuum degree is 7.5 × 10⁻⁶. 4 Pa, under conditions of 22A current and 900r / min copper roller spinning for 20s, yielded Mg. 40 Zn 40 Cu 12 Al8 precursor.

[0087] Step 4, Mg 40 Zn 40 Cu 12 The Al8 precursor was subjected to a first vacuum heat treatment in a vapor-phase dealloying system to obtain Mg, a copper-based intermetallic porous material with a bicontinuous structure. 30 Cu 42 A l 28 The conditions for the first vacuum heat treatment were a vacuum degree of 2 × 10⁻⁶. -4 Pa, heating rate of 9 K / min, temperature of 773 K, time of 3 hours.

[0088] Fifth, a portion of the product from step four is placed in a vapor-phase dealloying system for a second vacuum heat treatment to obtain Cu6Al4, a porous intermetallic compound material with a bicontinuous structure. The conditions for the second vacuum heat treatment are a vacuum degree of 1.5 × 10⁻⁶. -4 Pa, heating rate 11 K / min, temperature 700 K, time 5 hours.

[0089] Example 4

[0090] The first step involves weighing 30g of Mg, Zn, Cu and Si metal blocks according to the atomic ratio of Mg, Zn, Cu and Si in the MgZnCuSi alloy ingot of 40:40:16.67:3.33, to obtain the alloy precursor.

[0091] The second step involves placing the alloy precursor in a boron nitride crucible, then placing the boron nitride crucible inside an induction melting furnace. The induction melting furnace is then evacuated to a vacuum level of 3 × 10⁻⁶. -3 A current of 18 A was applied to Pa, and induction melting was performed for 120 s. After cooling, Mg was obtained. 40 Zn 40 (Cu5Si) 20 Alloy ingot.

[0092] Third step, take 3g of Mg 40 Zn 40 (Cu5Si) 20The alloy ingots are mechanically polished and placed in a strip spinning machine, which is then evacuated to a vacuum level of 6×10⁻⁶. -4 Pa, then argon gas is introduced into the belt spinning machine until the vacuum degree is 8.5 × 10⁻⁶. 4 Pa, under conditions of 26A current and 1100r / min copper roller speed, was spun for 30s to obtain Mg. 40 Zn 40 (Cu5Si) 20 Precursor.

[0093] Step 4, Mg 40 Zn 40 (Cu5Si) 20 The precursor was subjected to a first vacuum heat treatment in a vapor-phase dealloying system to obtain a copper-based intermetallic porous material Mg5Cu with a bicontinuous structure. 10 Si2. The conditions for the first vacuum heat treatment were a vacuum degree of 1.5 × 10⁻⁶. -4 Pa, heating rate 11 K / min, temperature 873 K, time 2 hours.

[0094] Fifth, a portion of the product from step four is placed in a vapor-phase dealloying system for a second vacuum heat treatment to obtain Cu5Si, a porous copper-based intermetallic compound with a bicontinuous structure. The conditions for the second vacuum heat treatment are a vacuum degree of 2 × 10⁻⁶. -4 Pa, heating rate 10 K / min, temperature 800 K, time 6 hours.

[0095] Example 5

[0096] The first step involves weighing 30g of Mg, Zn, Cu, and Al metal blocks according to the atomic ratio of Mg, Zn, Cu, and Al in the MgZnCuAl alloy ingot of 40:40:12:8, to obtain the alloy precursor.

[0097] The second step involves placing the alloy precursor in a boron nitride crucible, then placing the boron nitride crucible inside an induction melting furnace. The induction melting furnace is then evacuated to a vacuum level of 2 × 10⁻⁶. -3 A current of 22 A was applied to Pa, and induction melting was carried out for 90 seconds. After cooling, Mg was obtained. 40 Zn 40 Cu 12 Al8 alloy ingot.

[0098] Third step, take 3g of Mg 40 Zn 40 Cu 12 Al8 alloy ingots are mechanically polished and placed in a belt spinning machine, which is then evacuated to a vacuum level of 8 × 10⁻⁶. -4Pa, then argon gas is introduced into the belt spinning machine until the vacuum degree is 7.8 × 10⁻⁶. 4 Pa, under conditions of 25A current and 900r / min copper roller rotation speed, was spun for 21s to obtain Mg. 40 Zn 40 Cu 12 Al8 precursor.

[0099] Step 4, Mg 40 Zn 40 Cu 12 The Al8 precursor was subjected to a third vacuum heat treatment in a vapor-phase dealloying system to obtain Cu6Al4, a porous intermetallic compound material with a bicontinuous structure. The conditions for the third vacuum heat treatment were a vacuum degree of 2 × 10⁻⁶. -4 Pa, heating rate of 9 K / min, temperature of 773 K, time of 8 hours.

[0100] Comparative Example 1

[0101] The first step involves weighing 30g of Mg, Zn, Cu and Si metal blocks according to the atomic ratio of Mg, Zn, Cu and Si in the MgZnCuSi alloy ingot of 40:40:16.67:3.33, to obtain the alloy precursor.

[0102] The second step involves placing the alloy precursor in a boron nitride crucible, then placing the boron nitride crucible inside an induction melting furnace. The induction melting furnace is then evacuated to a vacuum level of 1×10⁻⁶. -3 A 20A induced current was applied, and induction melting was performed for 110s. After cooling, Mg was obtained. 40 Zn 40 (Cu5Si) 20 Alloy ingot.

[0103] Third step, take 3g of Mg 40 Zn 40 Cu 100 Si 20 The alloy ingots are mechanically polished and placed in a strip spinning machine, which is then evacuated to a vacuum level of 5×10⁻⁶. -4 Pa, then argon gas is introduced into the belt spinning machine until the vacuum degree is 8×10. 4 Pa, under conditions of 24A current and 1000r / min copper roller speed, was spun for 25s to obtain Mg. 40 Zn 40 (Cu5Si) 20 Precursor.

[0104] Step 4, Mg 40 Zn 40 (Cu5Si) 20The precursor was subjected to a first vacuum heat treatment in a vapor-phase dealloying system to obtain the product. The conditions for the first vacuum heat treatment were a vacuum degree of 6 × 10⁻⁶. -4 Pa, heating rate 10 K / min, temperature 733 K, time 4 hours.

[0105] Comparative Example 2

[0106] The first step involves weighing 30g of Mg, Zn, Cu and Si metal blocks according to the atomic ratio of Mg, Zn, Cu and Si in the MgZnCuSi alloy ingot of 40:40:16.67:3.33, to obtain the alloy precursor.

[0107] The second step involves placing the alloy precursor in a boron nitride crucible, then placing the boron nitride crucible inside an induction melting furnace. The induction melting furnace is then evacuated to a vacuum level of 1×10⁻⁶. -3 A 20A induced current was applied, and induction melting was performed for 110s. After cooling, Mg was obtained. 40 Zn 40 (Cu5Si) 20 Alloy ingot.

[0108] Third step, take 3g of Mg 40 Zn 40 (Cu5Si) 20 The alloy ingots are mechanically polished and placed in a strip spinning machine, which is then evacuated to a vacuum level of 5×10⁻⁶. -4 Pa, then argon gas is introduced into the belt spinning machine until the vacuum degree is 8×10. 4 Pa, under conditions of 24A current and 1000r / min copper roller speed, was spun for 25s to obtain Mg. 40 Zn 40 (Cu5Si) 20 Precursor.

[0109] Step 4, Mg 40 Zn 40 (Cu5Si) 20 The precursor was subjected to a first vacuum heat treatment in a vapor-phase dealloying system to obtain the product. The conditions for the first vacuum heat treatment were a vacuum degree of 1 × 10⁻⁶. -4 Pa, heating rate 10 K / min, temperature 500 K, time 4 hours.

[0110] Comparative Example 3

[0111] The first step involves weighing 30g of Mg, Zn, Cu and Si metal blocks according to the atomic ratio of Mg, Zn, Cu and Si in the MgZnCuSi alloy ingot of 40:40:16.67:3.33, to obtain the alloy precursor.

[0112] The second step involves placing the alloy precursor in a boron nitride crucible, then placing the boron nitride crucible inside an induction melting furnace. The induction melting furnace is then evacuated to a vacuum level of 1×10⁻⁶. -3 A 20A induced current was applied, and induction melting was performed for 110s. After cooling, Mg was obtained. 40 Zn 40 (Cu5Si) 20 Alloy ingot.

[0113] The third step is to add Mg 40 Zn 40 (Cu5Si) 20 The alloy ingot was placed in a vapor-phase dealloying system for a first vacuum heat treatment to obtain the product. The conditions for the first vacuum heat treatment were a vacuum degree of 1 × 10⁻⁶. -4 Pa, heating rate 10 K / min, temperature 733 K, time 4 hours.

[0114] Figure 2-a , 2-b Images 2-c show SEM images of cross-sections of MgZnCuAl precursor samples after vacuum heat treatment in a vapor-phase dealloying system for 2 hours, 4 hours, and 6 hours. The scale bar is 2 μm. Figure 2-a It can be seen that vapor-phase dealloying starts from the surface of the sample, and dealloying occurs first in regions I and III, forming defects and producing porous structures, while porous structures have not yet formed in the middle region II. Figure 2-b The three regions formed the MgCuAl phase, exhibiting a bicontinuous structure. Figure 2-c Further vapor-phase dealloying was carried out, and it was completely transformed into the CuAl phase, resulting in a uniform bicontinuous structure.

[0115] Figure 3 XRD patterns of the MgZnCuAl precursor at 693 K for different time periods during the dealloying process. The bottom blue layer (0h) is the XRD curve of the MgZnCuAl precursor; the dark green layer (2h) is the XRD curve of the coexistence of the MgZnCuAl precursor and porous MgCuAl during the dealloying process; the light green layer (4h) is the XRD curve of complete transformation into porous MgCuAl; the yellow layer (7h) is the XRD curve of the coexistence of porous MgCuAl and porous CuAl; and the orange layer (9h) and red layer (12h) are the XRD curves of complete transformation into porous CuAl. The peaks are characteristic peaks of the corresponding intermetallic compound Cu6Al4.

[0116] Figure 4-a The image shows a SEM image of the MgZnCuSi precursor, with a scale bar of 2 μm. It can be seen from the image that it does not possess a bicontinuous structure.

[0117] Figure 4-b The image shows an SEM image of MgCuSi with a scale bar of 2 μm. Based on this image, the characteristic size of the ligaments is calculated to be between 100 nm and 250 nm, with the largest number of ligaments at 200 nm. A bicontinuous structure can be seen in the image.

[0118] Figure 4-c The image shows a SEM image of CuSi with a scale bar of 2 μm. Based on this image, the characteristic size of the ligaments is calculated to be between 200 nm and 380 nm, with the largest number of ligaments at 350 nm. A bicontinuous structure can be seen in the image.

[0119] Figure 5 The XRD patterns of the MgZnCuSi precursor at 733 K for different time periods during the dealloying process are shown. The bottom purple layer (0h) is the XRD curve of the MgZnCuSi precursor, the blue layer (6h) is the XRD curve of the completely transformed porous MgCuSi, the dark green layer (10h) is the XRD curve of the coexistence of porous MgCuSi and porous CuSi, and the orange layer (12h) and red layer (16h) are the XRD curves of the completely transformed porous CuSi. The peaks are the characteristic peaks of the corresponding intermetallic compound Cu5Si.

[0120] Figure 6-a The image shows the surface SEM image of the product prepared in Comparative Example 1. Figure 6-b The images show internal SEM images of the products prepared in Comparative Example 1. No bicontinuous structure was formed in any of the images, indicating that when the pressure of vacuum heat treatment is insufficient, a bicontinuous structure with three-dimensional through-holes cannot be prepared. Instead, small pits are formed on or inside the sample, and their distribution is uneven.

[0121] Figure 7 The image shown is an SEM image of the product prepared in Comparative Example 2. The product also did not form a bicontinuous structure, indicating that when the temperature is too low, a bicontinuous structure with three-dimensional through-holes cannot be prepared. Instead, small pits are formed on or inside the sample, and the distribution is uneven.

[0122] Figure 8 The image shows the SEM image of the product prepared in Comparative Example 3. The product did not form a bicontinuous structure, indicating that when the sample is not subjected to a strip spinning process, the precursor components are not mixed evenly, making it difficult to prepare copper-based intermetallic porous materials with a bicontinuous structure.

[0123] The specific embodiments described above further illustrate the purpose, technical solution, and beneficial effects of the present invention. It should be understood that the above description is only a specific embodiment of the present invention and is not intended to limit the scope of protection of the present invention. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of the present invention should be included within the scope of protection of the present invention.

Claims

1. A method for preparing a copper-based intermetallic compound porous material, characterized in that, The preparation method includes: Metals Mg, Zn, Cu, and M are mixed and subjected to induction melting to obtain MgZnCuM alloy ingots; The MgZnCuM alloy ingot was subjected to a strip spinning process to obtain the MgZnCuM precursor; The MgZnCuM precursor was subjected to a first vacuum heat treatment in a vapor-phase dealloying system to obtain a copper-based intermetallic porous material MgCuM; the MgCuM has a bicontinuous structure.

2. The preparation method according to claim 1, characterized in that, After obtaining the copper-based intermetallic porous material MgCuM, the method further includes: The copper-based intermetallic porous material MgCuM is placed in the vapor-phase dealloying system for a second vacuum heat treatment to obtain copper-based intermetallic porous material CuM; the CuM has a bicontinuous structure.

3. The preparation method according to claim 1, characterized in that, After obtaining the MgZnCuM precursor, the process further includes: The MgZnCuM precursor was subjected to a third vacuum heat treatment in a vapor-phase dealloying system to obtain CuM, a copper-based intermetallic porous material; the CuM has a bicontinuous structure.

4. The preparation method according to claim 1, characterized in that, The conditions for the induction melting process are: induction current 18A-22A, vacuum degree 1×10⁻⁶. -3 Pa-3×10 -3 Pa; The conditions for the belt spinning process are: inert atmosphere, current 22A-26A, vacuum degree 7.5×10⁻⁶. 4 Pa -8.5×10 4 Pa, copper roller speed 900r / min-1100r / min, time 20s-30s.

5. The preparation method according to any one of claims 1-4, characterized in that, The MgZnCuM alloy ingot is Mg x Zn y (Cu3Al2) z Alloy ingot, wherein 30≤x≤40, 30≤y≤40, 20≤z≤40.

6. The preparation method according to claim 5, characterized in that, The conditions for the first vacuum heat treatment were: vacuum degree 1×10⁻⁶. -4 Pa-2×10 -4 Pa, heating rate of 9K / min-11K / min, temperature of 693K-773K, time of 3-6 hours.

7. The preparation method according to any one of claims 1-4, characterized in that, The MgZnCuM alloy ingot is Mg x Zn y (Cu5Si) z Alloy ingot, wherein 30≤x≤40, 30≤y≤40, 20≤z≤40.

8. The preparation method according to claim 7, characterized in that, The conditions for the first vacuum heat treatment were: vacuum degree 1×10⁻⁶. -4 Pa-2×10 -4 Pa, heating rate of 9K / min-11K / min, temperature of 733K-873K, time of 2-7 hours.

9. A copper-based intermetallic compound porous material, characterized in that, The copper-based intermetallic compound porous material is prepared by any one of the preparation methods described in claims 1-8.

10. An application of the copper-based intermetallic compound porous material according to claim 9, characterized in that, The copper-based intermetallic porous materials are used in glucose sensors or in catalytic reactions for carbon dioxide reduction.

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