CuZn nano-alloy confined framework induced by plasma-implanted long-range hole groups, and preparation method and application thereof

Abstract

This invention discloses a plasma-impregnated long-range pore group-induced confined framework of CuZn nanoalloys, its preparation method, and its applications. The catalyst material of this invention uses a covalent organic framework with long-range nanopores as a substrate. Cu and Zn ions are impregnated into the long-range nanopores of the substrate via plasma, and group induction is utilized to form a CuZn nanoalloy with high CO adsorption performance and low C-C coupling energy barrier. The CuZn nanoalloy is immobilized within the nanopores of the substrate by a confinement effect. The synthesis method of this catalyst material is simple, safe, and highly controllable. Furthermore, its catalytic electrochemical performance can be regulated by adjusting the ratio of the two metals in the CuZn alloy. It exhibits extremely high efficiency and selectivity in the electrochemical CO2RR application to generate C2H4. This electrocatalyst has a long service life and can be repeatedly recycled and reused, making it suitable for fields such as environmental functional materials, energy conversion and utilization.

Description

Technical Field

[0001] This invention belongs to the field of materials preparation, and particularly relates to a group-induced confined framework of CuZn nanoalloys induced by plasma-impregnated long-range channels, its preparation method, and its application. Background Technology

[0002] The CO2 electroreduction process is often limited by problems such as the variety of reduction products, the difficulty of in-depth reduction, and competition from the hydrogen production reaction by water electrolysis. Therefore, it is of paramount importance to develop efficient electrocatalysts with corresponding functions to address these problems and challenges.

[0003] Cu is widely considered one of the most promising metal species for C2 products. Long-range porous organic frameworks (LMBs) are extensively used as supported catalyst supports due to their large specific surface area and numerous well-defined loading sites. Therefore, Cu-based catalysts supported on LMBs are promising active catalysts for CO2RR to C2 products. However, the slow formation of the key intermediate *CO on Cu significantly limits the application of this type of catalyst. We theoretically and experimentally screened for a second metal, Zn, which, together with Cu, forms a nanoalloy phase. The CuZn nanoalloy phase effectively lowers the reduction barrier from CO2 to CO and exhibits strong *CO adsorption performance, providing abundant raw materials for subsequent coupling reactions to generate C2 products. Furthermore, the C-C coupling step determines the lower limit of C2 product production, and difficult coupling often leads to low C2 Faradaic efficiency. Therefore, we introduced functional groups to regulate the electronic properties of the CuZn nanoalloy phase, inducing the generation of interstitial electrons with low work function and high mobility, resulting in more efficient CO activation and C-C coupling, thereby achieving high selectivity for C2H4 products.

[0004] Here, we utilize plasma to implant metal ions into a long-range porous organic framework, stabilizing CuZn nanoalloys through confinement and thermal reduction. Simultaneously, we utilize functional groups to induce interstitial electrons in the CuZn nanoalloys, optimizing their electronic properties and achieving enhanced electrocatalytic performance of the plasma-implanted, long-range porous, functionally-induced CuZn nanoalloy confined framework. The plasma-implanted, long-range porous, functionally-induced CuZn nanoalloy confined framework efficiently reduces CO2 to C2H4, significantly improving energy utilization efficiency. The development of this material plays a crucial role in developing high-performance materials through nanoscale control and in addressing various environmental and energy application challenges caused by massive global CO2 emissions. In existing technologies, Chinese patent CN117101666A discloses a copper-zinc alloy catalyst, its preparation method, and its applications. However, its application involves the introduction of H2 and CO, both hazardous gases, and the reaction conditions are extremely dangerous, requiring high pressures of 3–5 MPa and high temperatures of 240–340 °C, with unsatisfactory conversion efficiency. This method only requires the introduction of non-toxic CO2 during the application process, and the reaction takes place at room temperature and pressure. Therefore, the preparation of highly efficient electrocatalysts that can be used under mild conditions is crucial. Summary of the Invention

[0005] To address the aforementioned problems in existing technologies, the present invention aims to provide a group-induced CuZn nano-alloy confined framework with plasma-impregnated long-range channels, its preparation method, and its applications. The synthesis method of the catalyst material of this invention is well-defined and controllable, with minimal pollution; the metal particles in the catalyst are uniform in size and well-dispersed. Through group induction and the synergistic effect of the CuZn alloy, the catalyst material of this invention exhibits highly efficient CO conversion adsorption and CC-coupled electrocatalytic performance. This electrocatalyst has a long service life and can be repeatedly recycled and reused.

[0006] To control the atomic ratio and stability of Cu and Zn in the catalyst material, this invention employs a plasma excitation method: utilizing the uniformity and confinement effect of the nanopores inherent in the long-range porous organic framework, uniformly sized and well-proportioned CuZn nanoalloys are obtained within the pores of the long-range porous organic framework through plasma excitation; simultaneously, the functional groups are located inside the pores of the long-range porous organic framework, thus achieving efficient preparation of catalysts containing functional group-induced CuZn nanoalloys.

[0007] In the process of synthesizing catalyst materials, the present invention uses a plasma exciter to excite metal ions to form metal plasma under heating, and then injects it into the channels of the organic framework with the introduced inert gas. The ratio of Cu and Zn in CuZn nanoalloy is controlled by the metal addition ratio in the metal salt solution.

[0008] This plasma-induced confined framework of CuZn nanoalloys with long-range pores utilizes a covalent organic framework with long-range pores as a substrate. Cu and Zn ions are implanted into the long-range pores of the substrate via plasma, and through group induction, CuZn nanoalloys with high CO adsorption capacity and low CC coupling barrier are formed. The CuZn nanoalloys are immobilized within the nanopores of the substrate by a confinement effect. The size of the nanopores is on the nanometer scale, the doping level of the CuZn alloy is on the nanometer scale, and the size of the CuZn alloy is smaller than the size of the pores. The molar ratio of Cu to Zn is 1 to 2:1, preferably 1 to 1.2:1. The covalent organic framework substrate is polymerized from 1,3,5-tris(4-aminophenyl)benzene monomer and terephthalaldehyde ligand or substituted terephthalaldehyde ligand (the reaction mechanism is a condensation reaction between the amino group of the monomer and the aldehyde group of the ligand). The substituents on the benzene ring of the substituted terephthalaldehyde include at least one of hydroxyl (OH) and methoxy (OCH3). The groups are derived from H on the benzene ring of the ligand or H and H substituents on the benzene ring of the ligand. That is, the types of groups include hydrogen atom (H), or hydrogen atom (H) and hydroxyl (OH), or hydrogen atom (H) and methoxy (OCH3).

[0009] Furthermore, the method for preparing the covalent organic framework substrate includes the following steps:

[0010] 1) Add 1,3,5-tris(4-aminophenyl)benzene monomer, ligand, methanol and glacial acetic acid (part 1) to a solvent and mix. Stir the mixture at room temperature for 4-6 hours. The ligand is substituted terephthalaldehyde, and the substituent group on the benzene ring of the substituted terephthalaldehyde is H, hydroxyl OH or methoxy OCH3. The molar ratio of ligand to monomer is 1.1-2:1. The volume of methanol is 8-12 times the volume of glacial acetic acid (part 1), the volume of solvent is 10-25 times the volume of methanol, and the feed ratio of monomer to glacial acetic acid (part 1) is 1 mmol: 1-1.5 mL.

[0011] 2) Add the second part of glacial acetic acid to the reaction solution in step 1) and heat to 40-60°C to react. After the reaction is completed, centrifuge to obtain a solid, and then wash and dry it to obtain the covalent organic framework substrate.

[0012] Further, in step 1), the ligand includes at least one of terephthalaldehyde, 2,5-dihydroxyterephthalaldehyde and 2,5-dimethoxybenzene-1,4-dicarboxaldehyde, and the molar ratio of the ligand to the monomer is 1.5-2.0:1.

[0013] Further, in step 1), the solvent is a mixture of 1,4-dioxane / butanol, with a volume ratio of 0.5 to 1.5:1, preferably 1:1; the volume of the solvent is 15 to 20 times that of methanol. 1,4-dioxane / butanol is the solvent in the preparation of the long-range porous organic framework and serves as the reaction site. Methanol and glacial acetic acid act as catalysts, catalyzing the polymerization of monomer 1,3,5-tris(4-aminophenyl)benzene and ligands into the long-range porous organic framework.

[0014] Furthermore, the reaction time for stirring at room temperature in step 1) is 5-5.5 h;

[0015] Furthermore, in step 2), the heating temperature is 50-55℃, and the heating reaction time is 20-28h, preferably 24h.

[0016] Furthermore, the volume of the second portion of glacial acetic acid in step 2) is 5-20 times, preferably 8-12 times, the volume of the first portion of glacial acetic acid in step 1).

[0017] The method for preparing a group-induced confined framework of CuZn nano-alloys with plasma-impregnated long-range channels includes the following steps: preparing a mixed aqueous solution containing copper and zinc salts and adding it to the plasma excitation chamber of a plasma vapor deposition apparatus; loading the covalent organic framework substrate into a quartz boat; placing the quartz boat in a tube furnace that is in a sealed connection with the plasma excitation chamber; introducing argon gas; after exhausting the air in the plasma excitation chamber and the tube furnace; heating the plasma excitation chamber and the tube furnace; continuously heating and excitation; under heating, the plasma exciter excites metal ions to form metal plasma, which is then injected into the channels of the covalent organic framework substrate along with the introduced argon gas; maintaining the stability of the argon gas during this process; after cooling to room temperature, thoroughly washing the obtained covalent organic framework substrate with loaded ionic metals with water and ethanol, then drying it, and finally reducing it under an H2 / Ar gas flow to obtain the group-induced confined framework of CuZn nano-alloys with plasma-impregnated long-range channels.

[0018] Preferably, the long-range pore organic framework has a size in the micrometer range (0.1-1 μm) and the pore size is in the nanometer range, in order to unify the size of the metal nano-alloy.

[0019] Preferably, based on the addition amount of the covalent organic framework substrate being 50 mg, the total addition amount of copper salt and zinc salt is 10-20 mg, preferably 15 mg; the metal molar ratio of Cu to Zn is 1-2:1, preferably 1-1.2:1.

[0020] Preferably, argon gas is continuously introduced to drive the metal plasma excited in the plasma excitation chamber into the pores of the long-path organic framework, while removing oxygen in the reaction environment to prevent oxidation. Based on the dosage of the covalent organic framework substrate being 50 mg, the argon gas flow rate is 10-30 ml / min, preferably 20 ml / min.

[0021] Preferably, the plasma excitation chamber and the tube furnace are heated simultaneously and continuously to ensure that the metal plasma maintains its plasma state throughout the entire process of driving the hole. The temperature is set to 300-500℃, preferably 400℃; the heating time is 2-4 hours, preferably 3 hours.

[0022] Preferably, the impregnated sample is thoroughly washed with water and ethanol in order to remove the metal species adsorbed on the surface.

[0023] Preferably, the reduction under H2 / Ar gas flow is used to reduce Cu ions and Zn ions to the metallic state to form an alloy. During the reduction process, the volume fraction of H2 in the H2 / Ar gas flow is 5-15%, preferably 10%. The reduction temperature under H2 / Ar gas flow is 150-300℃, preferably 200℃; the reduction time is 1-3 hours, preferably 2 hours.

[0024] This invention also provides the catalytic application of the group-induced confined framework of CuZn nanoalloys induced by plasma-impregnated long-range channels in the CO2 reduction reaction to produce C2H4.

[0025] The plasma-impregnated long-range channel group-induced confined CuZn nano-alloy framework of the present invention has the following advantages in practical use:

[0026] 1. Compared with conventional electrochemical catalysts used in CO2RR, the plasma-impregnated long-range channel CuZn nano-alloy confined framework of this invention not only improves the performance of catalytic CO production and adsorption, but also significantly reduces the subsequent CC coupling barrier, thus facilitating C2H4 production. Secondly, the plasma-impregnated long-range channel CuZn nano-alloy confined framework of this invention exhibits high stability. The metal within the long-range channel organic framework is a nanoscale alloy phase, stabilized by the confinement effect of the long-range channel organic framework. Furthermore, the functional groups induce the generation of interstitial electrons in the CuZn nano-alloy, regulating its electronic properties. The material as a whole possesses extremely high stability, thus exhibiting a long service life and extremely high catalytic activity.

[0027] 2. Compared with the preparation of traditional nano-alloy catalysts, the plasma-impregnated long-range channel group-induced CuZn nano-alloy confined framework preparation method of the present invention has high controllability, is simple and safe, and produces uniformly sized CuZn nano-alloys. Furthermore, the proportion of different metals in the alloy can be controlled by varying the amount of metal added. Studies have found that the plasma-impregnated long-range channel group-induced CuZn nano-alloy confined framework of the present invention can catalyze the CO2 reduction reaction to C2H4 with extremely high selectivity and efficiency.

[0028] 3. Since the CuZn nano-alloy confined framework induced by the plasma-impregnated long-range channels of the present invention has the characteristics of simple method, high controllability and safety, simultaneous improvement of catalytic selectivity and efficiency, reusability and long life, it has great potential in the energy and other fields. Attached Figure Description

[0029] Figure 1 This is a scanning electron microscope image of the CuZn nanoalloy confined framework induced by plasma-impregnated long-range channels prepared in Example 2.

[0030] Figure 2 This is a scanning electron microscope image of the CuZn nanoalloy confined framework induced by plasma-impregnated long-range channels prepared in Example 5.

[0031] Figure 3 This is a scanning electron microscope (SEM) image of the confined framework of CuZn nanoalloys induced by plasma-impregnated long-range channels obtained in Example 8. Detailed Implementation

[0032] The present invention will be further described below with reference to specific embodiments, but the scope of protection of the present invention is not limited thereto.

[0033] In the following embodiments, the preparation method of the long-range porous organic framework is as follows: 1,3,5-tris(4-aminophenyl)benzene, ligand, 1,4-dioxane / butanol, methanol, and glacial acetic acid are mixed in a glass bottle and reacted by stirring at room temperature; then glacial acetic acid is added and the reaction is heated. The solid is obtained by centrifugation, then thoroughly washed with tetrahydrofuran and acetone, and dried under vacuum to obtain the long-range porous organic framework. In the following embodiments, this long-range porous organic framework is used to prepare a CuZn nano-alloy confined framework induced by plasma-impregnated long-range pore groups.

[0034] Of course, those skilled in the art should know that the method for preparing this long-range porous organic framework is only a preferred embodiment of the present invention, and the parameters can be adjusted according to actual needs. The long-range porous organic framework can also utilize other porous covalent organic framework substrates with adsorption properties found in the prior art.

[0035] The catalyst of this invention is prepared by a Schiff base reaction to create a long-range porous organic framework, which is then immobilized as a CuZn nano-alloy using a plasma-induced method to utilize the confinement effect of the pores. The formation of the metal alloy phase is achieved through reduction. After metal plasma is implanted into the pores of the long-range porous organic framework, a CuZn nano-alloy confinement framework induced by the plasma-implanted groups in a reducing gas atmosphere is formed in a tube furnace. After the same steps, the CuZn nano-alloy is immobilized within the pores of the long-range porous organic framework. Specific embodiments are as follows:

[0036] Example 1

[0037] In this embodiment, the specific steps for preparing the group-induced confined framework of CuZn nanoalloys with plasma-impregnated long-range channels are as follows:

[0038] (1) Add 0.4 mmol of 1,3,5-tris(4-aminophenyl)benzene, 0.75 mmol of terephthalaldehyde, 1,4-dioxane / butanol (50 / 50 ml), 5 ml of methanol and 0.5 ml of glacial acetic acid to a glass bottle, and then stir the resulting solution at room temperature for 5 h.

[0039] (2) Add 5 ml of glacial acetic acid to the solution obtained in step (1) and heat to 50°C for 24 h;

[0040] (3) Filter the solution obtained in step (2), wash the obtained solid substance thoroughly with tetrahydrofuran and acetone, and dry it under vacuum at 50°C to obtain a long-range pore organic framework with coordinated groups.

[0041] (4) Prepare a mixed aqueous solution containing a total of 15 mg of copper chloride and zinc chloride, wherein the molar ratio of Cu to Zn is 0.5:1, and add it to the plasma excitation chamber of the plasma vapor deposition device;

[0042] (5) Weigh 50 mg of the long-path organic framework with group coordination using a quartz boat and place it in a tube furnace that is in a closed connection with the plasma excitation chamber.

[0043] (6) Argon gas is introduced and flows through the plasma excitation chamber and the tube furnace (the same below) in sequence at a flow rate of 20 ml / min. After the air in the excitation chamber and the tube furnace is exhausted, the plasma excitation chamber and the tube furnace are heated synchronously (the heating temperature of both is the same, the same below). The plasma exciter excites metal ions to form metal plasma under heating and is injected into the channels of the organic framework with the introduced inert gas. The excitation is continuously heated at 400℃ for 3 hours. During this process, the argon gas is kept stable and the copper chloride and zinc chloride are completely volatilized.

[0044] (7) After cooling to room temperature, the long-range porous organic framework is thoroughly cleaned with water and ethanol. The obtained long-range porous organic framework containing ionic metal is dried to remove the metal ions on the surface, thus obtaining a pore-confined CuZn ion-loaded long-range porous organic framework.

[0045] (8) The CuZn ion-loaded long-range pore organic framework obtained in step (7) is reduced at 200°C for 2 hours under H2 / Ar gas flow (H2 volume fraction is 10%) to obtain a CuZn nano-alloy confined framework induced by plasma-impregnated long-range pore groups.

[0046] Example 2

[0047] In this embodiment, the specific steps for preparing the group-induced confined framework of CuZn nanoalloys with plasma-impregnated long-range channels are as follows:

[0048] (1) Add 0.4 mmol of 1,3,5-tris(4-aminophenyl)benzene, 0.75 mmol of terephthalaldehyde, 1,4-dioxane / butanol (50 / 50 ml), 5 ml of methanol and 0.5 ml of glacial acetic acid to a glass bottle, and then stir the resulting solution at room temperature for 5 h.

[0049] (2) Add 5 ml of glacial acetic acid to the solution obtained in step (1) and heat to 50°C for 24 h;

[0050] (3) Filter the solution obtained in step (2), wash the obtained solid substance thoroughly with tetrahydrofuran and acetone, and dry it under vacuum at 50°C to obtain a long-range pore organic framework with coordinated groups.

[0051] (4) Prepare a mixed aqueous solution containing a total of 15 mg of copper chloride and zinc chloride, wherein the molar ratio of Cu to Zn is 1:1, and add it to the plasma excitation chamber of the plasma vapor deposition device;

[0052] (5) Weigh 50 mg of the long-path organic framework with group coordination using a quartz boat and place it in a tube furnace that is in a closed connection with the plasma excitation chamber.

[0053] (6) Introduce argon gas at a flow rate of 20 ml / min. After the air in the excitation chamber and the tube furnace is exhausted, heat the plasma excitation chamber and the tube furnace simultaneously. Continue heating and excitation at 400°C for 3 hours. Keep the argon gas stable during this process.

[0054] (7) After cooling to room temperature, the long-range porous organic framework is thoroughly cleaned with water and ethanol. The obtained long-range porous organic framework containing ionic metal is dried to remove the metal ions on the surface, thus obtaining a pore-confined CuZn ion-loaded long-range porous organic framework.

[0055] (8) The CuZn ion-loaded long-range pore organic framework obtained in step (7) is reduced at 200°C for 2 hours under H2 / Ar gas flow (H2 volume fraction is 10%) to obtain a CuZn nano-alloy confined framework induced by plasma-impregnated long-range pore groups.

[0056] Example 3

[0057] In this embodiment, the specific steps for preparing the group-induced confined framework of CuZn nanoalloys with plasma-impregnated long-range channels are as follows:

[0058] (1) Add 0.4 mmol of 1,3,5-tris(4-aminophenyl)benzene, 0.75 mmol of terephthalaldehyde, 1,4-dioxane / butanol (50 / 50 ml), 5 ml of methanol and 0.5 ml of glacial acetic acid to a glass bottle, and then stir the resulting solution at room temperature for 5 h.

[0059] (2) Add 5 ml of glacial acetic acid to the solution obtained in step (1) and heat to 50°C for 24 h;

[0060] (3) Filter the solution obtained in step (2), wash the obtained solid substance thoroughly with tetrahydrofuran and acetone, and dry it under vacuum at 50°C to obtain a long-range pore organic framework with coordinated groups.

[0061] (4) Prepare a mixed aqueous solution containing a total amount of 15 mg of copper chloride and zinc chloride, wherein the molar ratio of Cu to Zn is 2:1, and add it to the plasma excitation chamber of the plasma vapor deposition device;

[0062] (5) Weigh 50 mg of the long-path organic framework with group coordination using a quartz boat and place it in a tube furnace that is in a closed connection with the plasma excitation chamber.

[0063] (6) Introduce argon gas at a flow rate of 20 ml / min. After the air in the excitation chamber and the tube furnace is exhausted, heat the plasma excitation chamber and the tube furnace simultaneously. Continue heating and excitation at 400°C for 3 hours. Keep the argon gas stable during this process.

[0064] (7) After cooling to room temperature, the long-range porous organic framework is thoroughly cleaned with water and ethanol. The obtained long-range porous organic framework containing ionic metal is dried to remove the metal ions on the surface, thus obtaining a pore-confined CuZn ion-loaded long-range porous organic framework.

[0065] (8) The CuZn ion-loaded long-range pore organic framework obtained in step (7) is reduced at 200°C for 2 hours under H2 / Ar gas flow (H2 volume fraction is 10%) to obtain a CuZn nano-alloy confined framework induced by plasma-impregnated long-range pores.

[0066] Example 4

[0067] In this embodiment, the specific steps for preparing the group-induced confined framework of CuZn nanoalloys with plasma-impregnated long-range channels are as follows:

[0068] (1) Add 0.4 mmol of 1,3,5-tris(4-aminophenyl)benzene, 0.75 mmol of 2,5-dihydroxyterephthalaldehyde, 1,4-dioxane / butanol (50 / 50 ml), 5 ml of methanol and 0.5 ml of glacial acetic acid to a glass bottle, and then stir the resulting solution at room temperature for 5 h.

[0069] (2) Add 5 ml of glacial acetic acid to the solution obtained in step (1) and heat to 50°C for 24 h;

[0070] (3) Filter the solution obtained in step (2), wash the obtained solid substance thoroughly with tetrahydrofuran and acetone, and dry it under vacuum at 50°C to obtain a long-range pore organic framework with coordinated groups.

[0071] (4) Prepare a mixed aqueous solution containing a total of 15 mg of copper chloride and zinc chloride, wherein the molar ratio of Cu to Zn is 0.5:1, and add it to the plasma excitation chamber of the plasma vapor deposition device;

[0072] (5) Weigh 50 mg of the long-path organic framework with group coordination using a quartz boat and place it in a tube furnace that is in a closed connection with the plasma excitation chamber.

[0073] (6) Introduce argon gas at a flow rate of 20 ml / min. After the air in the excitation chamber and the tube furnace is exhausted, heat the plasma excitation chamber and the tube furnace simultaneously. Continue heating and excitation at 400°C for 3 hours. Keep the argon gas stable during this process.

[0074] (7) After cooling to room temperature, the long-range porous organic framework is thoroughly cleaned with water and ethanol. The obtained long-range porous organic framework containing ionic metal is dried to remove the metal ions on the surface, thus obtaining a pore-confined CuZn ion-loaded long-range porous organic framework.

[0075] (8) The CuZn ion-loaded long-range pore organic framework obtained in step (7) is reduced at 200°C for 2 hours under H2 / Ar gas flow (H2 volume fraction is 10%) to obtain a CuZn nano-alloy confined framework induced by plasma-impregnated long-range pores.

[0076] Example 5

[0077] In this embodiment, the specific steps for preparing the group-induced confined framework of CuZn nanoalloys with plasma-impregnated long-range channels are as follows:

[0078] (1) Add 0.4 mmol of 1,3,5-tris(4-aminophenyl)benzene, 0.75 mmol of 2,5-dihydroxyterephthalaldehyde, 1,4-dioxane / butanol (50 / 50 ml), 5 ml of methanol and 0.5 ml of glacial acetic acid to a glass bottle, and then stir the resulting solution at room temperature for 5 h.

[0079] (2) Add 5 ml of glacial acetic acid to the solution obtained in step (1) and heat to 50°C for 24 h;

[0080] (3) Filter the solution obtained in step (2), wash the obtained solid substance thoroughly with tetrahydrofuran and acetone, and dry it under vacuum at 50°C to obtain a long-range pore organic framework with coordinated groups.

[0081] (4) Prepare a mixed aqueous solution containing a total of 15 mg of copper chloride and zinc chloride, wherein the molar ratio of Cu to Zn is 1:1, and add it to the plasma excitation chamber of the plasma vapor deposition device;

[0082] (5) Weigh 50 mg of the long-path organic framework with group coordination using a quartz boat and place it in a tube furnace that is in a closed connection with the plasma excitation chamber.

[0083] (6) Introduce argon gas at a flow rate of 20 ml / min. After the air in the excitation chamber and the tube furnace is exhausted, heat the plasma excitation chamber and the tube furnace simultaneously. Continue heating and excitation at 400°C for 3 hours. Keep the argon gas stable during this process.

[0084] (7) After cooling to room temperature, the long-range porous organic framework is thoroughly cleaned with water and ethanol. The obtained long-range porous organic framework containing ionic metal is dried to remove the metal ions on the surface, thus obtaining a pore-confined CuZn ion-loaded long-range porous organic framework.

[0085] (8) The CuZn ion-loaded long-range pore organic framework obtained in step (7) is reduced at 200°C for 2 hours under H2 / Ar gas flow (H2 volume fraction is 10%) to obtain a CuZn nano-alloy confined framework induced by plasma-impregnated long-range pores.

[0086] Example 6

[0087] In this embodiment, the specific steps for preparing the group-induced confined framework of CuZn nanoalloys with plasma-impregnated long-range channels are as follows:

[0088] (1) Add 0.4 mmol of 1,3,5-tris(4-aminophenyl)benzene, 0.75 mmol of 2,5-dihydroxyterephthalaldehyde, 1,4-dioxane / butanol (50 / 50 ml), 5 ml of methanol and 0.5 ml of glacial acetic acid to a glass bottle, and then stir the resulting solution at room temperature for 5 h.

[0089] (2) Add 5 ml of glacial acetic acid to the solution obtained in step (1) and heat to 50°C for 24 h;

[0090] (3) Filter the solution obtained in step (2), wash the obtained solid substance thoroughly with tetrahydrofuran and acetone, and dry it under vacuum at 50°C to obtain a long-range pore organic framework with coordinated groups.

[0091] (4) Prepare a mixed aqueous solution containing a total amount of 15 mg of copper chloride and zinc chloride, wherein the molar ratio of Cu to Zn is 2:1, and add it to the plasma excitation chamber of the plasma vapor deposition device;

[0092] (5) Weigh 50 mg of the long-path organic framework with group coordination using a quartz boat and place it in a tube furnace that is in a closed connection with the plasma excitation chamber.

[0093] (6) Introduce argon gas at a flow rate of 20 ml / min. After the air in the excitation chamber and the tube furnace is exhausted, heat the plasma excitation chamber and the tube furnace simultaneously. Continue heating and excitation at 400°C for 3 hours. Keep the argon gas stable during this process.

[0094] (7) After cooling to room temperature, the long-range porous organic framework is thoroughly cleaned with water and ethanol. The obtained long-range porous organic framework containing ionic metal is dried to remove the metal ions on the surface, thus obtaining a pore-confined CuZn ion-loaded long-range porous organic framework.

[0095] (8) The CuZn ion-loaded long-range pore organic framework obtained in step (7) is reduced at 200°C for 2 hours under H2 / Ar gas flow (H2 volume fraction is 10%) to obtain a CuZn nano-alloy confined framework induced by plasma-impregnated long-range pores.

[0096] Example 7

[0097] In this embodiment, the specific steps for preparing the group-induced confined framework of CuZn nanoalloys with plasma-impregnated long-range channels are as follows:

[0098] (1) Add 0.4 mmol of 1,3,5-tris(4-aminophenyl)benzene, 0.75 mmol of 2,5-dimethoxybenzene-1,4-dicarboxaldehyde, 1,4-dioxane / butanol (50 / 50 ml), 5 ml of methanol and 0.5 ml of glacial acetic acid to a glass bottle, and then stir the resulting solution at room temperature for 5 h.

[0099] (2) Add 5 ml of glacial acetic acid to the solution obtained in step (1) and heat to 50°C for 24 h;

[0100] (3) Filter the solution obtained in step (2), wash the obtained solid substance thoroughly with tetrahydrofuran and acetone, and dry it under vacuum at 50°C to obtain a long-range pore organic framework with coordinated groups.

[0101] (4) Prepare a mixed aqueous solution containing a total of 15 mg of copper chloride and zinc chloride, wherein the molar ratio of Cu to Zn is 0.5:1, and add it to the plasma excitation chamber of the plasma vapor deposition device;

[0102] (5) Weigh 50 mg of the long-path organic framework with group coordination using a quartz boat and place it in a tube furnace that is in a closed connection with the plasma excitation chamber.

[0103] (6) Introduce argon gas at a flow rate of 20 ml / min. After the air in the excitation chamber and the tube furnace is exhausted, heat the plasma excitation chamber and the tube furnace simultaneously. Continue heating and excitation at 400°C for 3 hours. Keep the argon gas stable during this process.

[0104] (7) After cooling to room temperature, the long-range porous organic framework is thoroughly cleaned with water and ethanol. The obtained long-range porous organic framework containing ionic metal is dried to remove the metal ions on the surface, thus obtaining a pore-confined CuZn ion-loaded long-range porous organic framework.

[0105] (8) The CuZn ion-loaded long-range pore organic framework obtained in step (7) is reduced at 200°C for 2 hours under H2 / Ar gas flow (H2 volume fraction is 10%) to obtain a CuZn nano-alloy confined framework induced by plasma-impregnated long-range pores.

[0106] Example 8

[0107] In this embodiment, the specific steps for preparing the group-induced confined framework of CuZn nanoalloys with plasma-impregnated long-range channels are as follows:

[0108] (1) Add 0.4 mmol of 1,3,5-tris(4-aminophenyl)benzene, 0.75 mmol of 2,5-dimethoxybenzene-1,4-dicarboxaldehyde, 1,4-dioxane / butanol (50 / 50 ml), 5 ml of methanol and 0.5 ml of glacial acetic acid to a glass bottle, and then stir the resulting solution at room temperature for 5 h.

[0109] (2) Add 5 ml of glacial acetic acid to the solution obtained in step (1) and heat to 50°C for 24 h;

[0110] (3) Filter the solution obtained in step (2), wash the obtained solid substance thoroughly with tetrahydrofuran and acetone, and dry it under vacuum at 50°C to obtain a long-range pore organic framework with coordinated groups.

[0111] (4) Prepare a mixed aqueous solution containing a total of 15 mg of copper chloride and zinc chloride, wherein the molar ratio of Cu to Zn is 1:1, and add it to the plasma excitation chamber of the plasma vapor deposition device;

[0112] (5) Weigh 50 mg of the long-path organic framework with group coordination using a quartz boat and place it in a tube furnace that is in a closed connection with the plasma excitation chamber.

[0113] (6) Introduce argon gas at a flow rate of 20 ml / min. After the air in the excitation chamber and the tube furnace is exhausted, heat the plasma excitation chamber and the tube furnace simultaneously. Continue heating and excitation at 400°C for 3 hours. Keep the argon gas stable during this process.

[0114] (7) After cooling to room temperature, the long-range porous organic framework is thoroughly cleaned with water and ethanol. The obtained long-range porous organic framework containing ionic metal is dried to remove the metal ions on the surface, thus obtaining a pore-confined CuZn ion-loaded long-range porous organic framework.

[0115] (8) The CuZn ion-loaded long-range pore organic framework obtained in step (7) is reduced at 200°C for 2 hours under H2 / Ar gas flow (H2 volume fraction is 10%) to obtain a CuZn nano-alloy confined framework induced by plasma-impregnated long-range pores.

[0116] Scanning electron microscopy (SEM) images of the plasma-impregnated long-range channel-induced confined framework of CuZn nanoalloys prepared in Examples 2, 5, and 8 are shown below. Figure 1 , Figure 2 and Figure 3 As shown, the skeleton induced by different groups has certain changes in shape. The stronger the electron-donating property of the group, the rougher the shape.

[0117] Example 9

[0118] In this embodiment, the specific steps for preparing the group-induced confined framework of CuZn nanoalloys with plasma-impregnated long-range channels are as follows:

[0119] (1) Add 0.4 mmol of 1,3,5-tris(4-aminophenyl)benzene, 0.75 mmol of 2,5-dimethoxybenzene-1,4-dicarboxaldehyde, 1,4-dioxane / butanol (50 / 50 ml), 5 ml of methanol and 0.5 ml of glacial acetic acid to a glass bottle, and then stir the resulting solution at room temperature for 5 h.

[0120] (2) Add 5 ml of glacial acetic acid to the solution obtained in step (1) and heat to 50°C for 24 h;

[0121] (3) Filter the solution obtained in step (2), wash the obtained solid substance thoroughly with tetrahydrofuran and acetone, and dry it under vacuum at 50°C to obtain a long-range pore organic framework with coordinated groups.

[0122] (4) Prepare a mixed aqueous solution containing a total amount of 15 mg of copper chloride and zinc chloride, wherein the molar ratio of Cu to Zn is 2:1, and add it to the plasma excitation chamber of the plasma vapor deposition device;

[0123] (5) Weigh 50 mg of the long-path organic framework with group coordination using a quartz boat and place it in a tube furnace that is in a closed connection with the plasma excitation chamber.

[0124] (6) Introduce argon gas at a flow rate of 20 ml / min. After the air in the excitation chamber and the tube furnace is exhausted, heat the plasma excitation chamber and the tube furnace simultaneously. Continue heating and excitation at 400°C for 3 hours. Keep the argon gas stable during this process.

[0125] (7) After cooling to room temperature, the long-range porous organic framework is thoroughly cleaned with water and ethanol. The obtained long-range porous organic framework containing ionic metal is dried to remove the metal ions on the surface, thus obtaining a pore-confined CuZn ion-loaded long-range porous organic framework.

[0126] (8) The CuZn ion-loaded long-range pore organic framework obtained in step (7) is reduced at 200°C for 2 hours under H2 / Ar gas flow (H2 volume fraction is 10%) to obtain a CuZn nano-alloy confined framework induced by plasma-impregnated long-range pores.

[0127] Compare with Example 1:

[0128] In this comparative example, only steps (4), (5), and (6) of Example 2 were changed to the following steps, while the remaining steps remained unchanged:

[0129] (4) Prepare a mixed aqueous solution containing a total of 15 mg of copper chloride and zinc chloride, wherein the molar ratio of Cu to Zn is 1:1;

[0130] (5) Weigh 50 mg of the long-path organic framework with group coordination, stir it in the aqueous solution of step (4) for 3 h, centrifuge to obtain solid material, dry it and place it in a tube furnace;

[0131] (6) Introduce argon gas at a flow rate of 20 ml / min. After the air in the tube furnace is exhausted, turn on the tube furnace heating device and heat continuously at 400°C for 3 hours. During this process, keep the argon gas stable.

[0132] Compare with Example 2:

[0133] In this comparative example, only steps (4), (5), and (6) of Example 5 were changed to the following steps, while the remaining steps remained unchanged:

[0134] (4) Prepare a mixed aqueous solution containing a total of 15 mg of copper chloride and zinc chloride, wherein the molar ratio of Cu to Zn is 1:1;

[0135] (5) Weigh 50 mg of the long-path organic framework with group coordination, stir it in the aqueous solution of step (4) for 3 h, centrifuge to obtain solid material, dry it and place it in a tube furnace;

[0136] (6) Introduce argon gas at a flow rate of 20 ml / min. After the air in the tube furnace is exhausted, turn on the tube furnace heating device and heat continuously at 400°C for 3 hours. During this process, keep the argon gas stable.

[0137] Compare with Example 3:

[0138] In this comparative example, only steps (4), (5), and (6) of Example 8 were changed to the following steps, while the remaining steps remained unchanged:

[0139] (4) Prepare a mixed aqueous solution containing a total of 15 mg of copper chloride and zinc chloride, wherein the molar ratio of Cu to Zn is 1:1;

[0140] (5) Weigh 50 mg of the long-path organic framework with group coordination, stir it in the aqueous solution of step (4) for 3 h, centrifuge to obtain solid material, dry it and place it in a tube furnace;

[0141] (6) Introduce argon gas at a flow rate of 20 ml / min. After the air in the tube furnace is exhausted, turn on the tube furnace heating device and heat continuously at 400°C for 3 hours. During this process, keep the argon gas stable.

[0142] Application Examples

[0143] Using the plasma-induced CuZn nano-alloy confined framework obtained in Examples 1-9 and the organic framework obtained in Control Examples 1-3 as catalysts, the CO2 electrochemical reduction reaction to generate C2H4 was tested.

[0144] The experimental conditions were as follows: 3 mg of catalyst was weighed and added to 300 μL of isopropanol, followed by 50 μL of Nafion. The mixture was sonicated for 30 min to obtain a uniformly dispersed catalyst-like ink. 150 μL of the ink-like ink was sprayed onto the hydrophilic side of a 0.75 cm × 2 cm hydrophobic carbon paper to obtain the cathode electrode. The anode was a 0.75 cm × 2 cm carbon paper. The anode and cathode chambers were separated by an ion exchange membrane. The cathode chamber was divided into two small spaces by the cathode electrode. CO2 gas was continuously introduced into the small space on the back of the cathode at a flow rate of 10 ml / min. The other small space in the cathode chamber and the anode chamber contained electrolyte, which was a 0.5 M potassium bicarbonate aqueous solution saturated with adsorbed CO2. CO2 reduction reaction tests were conducted on an electrochemical workstation at a voltage of -0.6 to -1.2 V. During the reaction, the electrolyte was circulated by a peristaltic pump. The yield of CO2 reduction products was monitored online using GC-MS, and the FE yield was determined based on the C2H4 production. C2H4 Calculate the potentials used in the experiment, replacing all potentials with the standard hydrogen electrode (RHE): E(RHE) = E(Ag / AgCl) + (0.21 + 0.059pH).

[0145] The confined CuZn nano-alloy frameworks prepared by plasma-impregnated long-range channels in different embodiments were subjected to CO2 reduction reactions at different test voltages on an electrochemical workstation for 3 hours. The tail gas monitoring results are shown in Tables 1 and 4. As can be seen from Table 1, the confined CuZn nano-alloy frameworks prepared by plasma-impregnated long-range channels in Examples 1-9 all exhibit ethylene selectivity at voltages of -0.9V, -1.0V, and -1.1V, i.e., the ethylene Faraday efficiency is not 0. Among them, all embodiments have the highest ethylene Faraday efficiency at -1.1V.

[0146] In Example 5, the ligand was 2,5-dihydroxyterephthalaldehyde, and the Cu / Zn ratio was 1:1. The plasma-impregnated long-range channel-induced confined framework of CuZn nanoalloys achieved the highest ethylene Faradaic efficiency at -0.9V, -1.0V, and -1.1V. After 3 hours of reaction, the Faradaic efficiencies at -0.9V, -1.0V, and -1.1V were 70.32%, 65.88%, and 80.38%, respectively. Furthermore, the reaction currents reached 102.5, 170.5, and 208.3 mA / cm², respectively. -2 This demonstrates that the synthesized CuZn nanoalloy confined framework induced by plasma-impregnated long-range channels possesses excellent catalytic activity.

[0147] Comparing the preparation processes of Examples 2, 5, and 8, when the Cu and Zn addition ratios were consistent (i.e., the alloy nanoparticle composition was the same), but the ligand groups were inconsistent, the performance of CuZn nanoalloys induced by groups with moderate electron-donating properties showed the most significant improvement in generating interstitial electrons. The catalytic efficiency of the confined framework of the synthesized CuZn nanoalloy induced by plasma-impacted long-range channels for the electrochemical reduction of CO2 to C2H4 first increased and then decreased with the electron-donating properties of the electron-donating groups. Comparing the preparation processes of Examples 4, 5, and 6, when the ligand groups were constant, increasing the Cu:Zn addition ratio from 1:1 to 2:1 or decreasing it to 0.5:1 resulted in a decrease in the catalytic efficiency of the confined framework of the synthesized CuZn nanoalloy induced by plasma-impacted long-range channels for the electrochemical reduction of CO2 to C2H4. Similarly, the same conclusions can be drawn by comparing Examples 1, 2, and 3, or Examples 7, 8, and 9. Therefore, it is evident that the plasma-impregnated long-range pores of the CuZn nano-alloy confined framework induced by the groups of this invention exhibit the best catalytic efficiency for the electrochemical reduction of CO2 to C2H4 under the induction of groups with moderate electron-donating properties. Furthermore, the optimal effect is achieved when the Cu to Zn addition ratio is 1:1, indicating that the moderate electron-donating group properties effectively induce and regulate the 1:1 CuZn alloy phase to a balanced state, which is beneficial to the entire reduction reaction process. The plasma-impregnated long-range pores of the CuZn nano-alloy confined framework of this invention enable highly efficient directional CO2RR to C2H4 production.

[0148] The experimental results of the control examples are shown in Tables 2 and 3. Compared with Examples 4, 5 and 6, the catalytic efficiency of the material prepared by the conventional impregnation method for the electrochemical reduction reaction of CO2 to generate C2H4 is much lower than that of the CuZn nano-alloy confined framework induced by the plasma-impregnated long-range channels of the present invention.

[0149] Table 1. Electrochemical reduction reaction of CO2 catalyzed by the confined framework of CuZn nanoalloys prepared by plasma-impregnated long-range channels in different embodiments, with FE content increasing after 3 h. C2H4 (%)

[0150]

[0151] Table 2. FE content of materials prepared from different control examples during 3 hours of catalytic CO2 electrochemical reduction reaction. C2H4 (%)

[0152]

[0153] Table 3 Current density (mA / cm²) of materials prepared from different control examples during the catalytic electrochemical reduction reaction of CO2. -2 )

[0154]

[0155] Table 4. Current density (mA / cm²) of CuZn nanoalloys with confined frameworks induced by plasma-impregnated long-range channels prepared in different embodiments during the electrochemical reduction reaction of CO2. -2 )

[0156]

[0157]

[0158] Example 5 demonstrates that it can maintain a current density and FE for over 15 hours during actual testing. C2H4 Stable. Furthermore, we conducted multiple repeat experiments; the catalyst electrode sheet in Example 5 could be used at least three times for 15 hours, with the current density and FE... C2H4 The electrocatalytic activity of the electrode sheet should not decrease significantly and should be maintained at least 60% of that of the fresh catalyst electrode.

[0159] The embodiments described above are merely preferred embodiments of the present invention and are not intended to limit the invention. For example, although one of the raw materials used in the preparation process in the above embodiments is 1,3,5-tris(4-aminophenyl)benzene, it does not mean that 1,3,5-tris(4-aminophenyl)benzene must be used to synthesize the material. As long as a carbon-based material containing three amino groups can be selected, and a porous organic framework can be generated, the excellent effects of the present invention can be achieved. For another example, the above embodiments only list the case where the Cu and Zn addition ratio is 0.5 to 2:1, but through experimentation, adjustments can be made within this range, for example, a Cu and Zn addition ratio of 0.7:1, which can also achieve the technical effects of the present invention. Furthermore, although the reducing gas used in the above embodiments reduces Cu and Zn ions, it does not mean that only reducing gas can achieve the effects of the present invention. Other reduction methods can be used to achieve the reduction effect of metal ions on a long-range porous organic framework, thus achieving the effects of the present invention.

[0160] The contents described in this specification are merely an enumeration of the implementation forms of the inventive concept, and the scope of protection of this invention should not be regarded as limited to the specific forms described in the embodiments.

Claims

1. A group-induced confined framework of CuZn nanoalloys induced by plasma-impregnated long-range channels, characterized in that, Using a covalent organic framework with long-range nanopores as a substrate, a plasma exciter excites metal ions to form metal plasma under heating, and then injects them into the long-range nanopores of the organic framework substrate with the introduced inert gas. By using group induction, a CuZn nanoalloy confined framework with improved CO adsorption performance and reduced CC coupling energy barrier is formed. The CuZn nanoalloy is fixed in the long-range nanopores of the substrate by the confinement effect. The molar ratio of Cu to Zn is 0.5~2 : 1; The types of groups include hydrogen atoms (H), or hydrogen atoms (H) and hydroxyl groups (OH), or hydrogen atoms (H) and methoxy groups (OCH3).

2. The group-induced confined framework of CuZn nanoalloys induced by plasma-impregnated long-range channels as described in claim 1, characterized in that, The CuZn nanoalloy is doped at the nanoscale, and the molar ratio of Cu to Zn is 1~1.2:

1. The covalent organic framework substrate is polymerized from 1,3,5-tris(4-aminophenyl)benzene monomer and terephthalaldehyde ligand or substituted terephthalaldehyde ligand. The substituents on the benzene ring of the substituted terephthalaldehyde include at least one of hydroxyl (OH) and methoxy (OCH3), and the groups are derived from H on the benzene ring of the ligand or H and H substituents on the benzene ring of the ligand.

3. The group-induced confined framework of CuZn nanoalloys induced by plasma-impregnated long-range channels as described in claim 1, characterized in that, The method for preparing the covalent organic framework substrate includes the following steps: 1) Add 1,3,5-tris(4-aminophenyl)benzene monomer, ligand, methanol and glacial acetic acid (part 1) to a solvent and mix. Stir the mixture at room temperature for 4-6 hours. The ligand is substituted terephthalaldehyde, and the substituent group on the benzene ring of the substituted terephthalaldehyde is H, hydroxyl OH or methoxy OCH3. The molar ratio of ligand to monomer is 1.1-2:

1. The volume of methanol is 8-12 times the volume of glacial acetic acid (part 1), the volume of solvent is 10-25 times the volume of methanol, and the feed ratio of monomer to glacial acetic acid (part 1) is 1 mmol: 1-1.5 mL. 2) Add the second part of glacial acetic acid to the reaction solution in step 1) and heat to 40~60℃ to react. After the reaction is completed, centrifuge to obtain a solid, and then wash and dry it to obtain the covalent organic framework substrate.

4. The group-induced confined framework of CuZn nanoalloys induced by plasma-impregnated long-range channels as described in claim 3, characterized in that, In step 1), the ligand includes at least one of terephthalaldehyde, 2,5-dihydroxyterephthalaldehyde, and 2,5-dimethoxybenzene-1,4-dicarboxaldehyde, and the molar ratio of the ligand to the monomer is 1.5-2.0:1; the solvent is a mixture of 1,4-dioxane / butanol, and the volume ratio of the two is 0.5-1.5:1; the volume of the solvent is 15-20 times the volume of methanol. The reaction time for stirring at room temperature in step 1) is 5-5.5 hours; In step 2), the heating temperature is 50-55℃, and the heating reaction time is 20-28h; In step 2), the volume of the second part of glacial acetic acid is 5-20 times that of the first part of glacial acetic acid in step 1).

5. The group-induced confined framework of CuZn nanoalloys induced by plasma-impregnated long-range channels as described in claim 4, characterized in that, In step 1), the volume ratio of 1,4-dioxane to butanol is 1:1; In step 2), the heating reaction time is 24 hours; In step 2), the volume of the second part of glacial acetic acid is 8-12 times that of the first part of glacial acetic acid in step 1).

6. The method for preparing a group-induced confined framework of CuZn nanoalloys via plasma-impregnated long-range channels as described in claim 1, characterized in that, Includes the following steps: A mixed aqueous solution containing copper and zinc salts was prepared and added to the plasma excitation chamber of a plasma vapor deposition apparatus. The covalent organic framework substrate was placed in a quartz boat, which was then placed in a tube furnace that was in a sealed connection with the plasma excitation chamber. Argon gas was introduced to purge the air from the plasma excitation chamber and the tube furnace. The plasma excitation chamber and the tube furnace were then heated and continuously excited. Under heating, the plasma exciter excited metal ions to form metal plasma, which was then injected into the pores of the covalent organic framework substrate along with the introduced argon gas. During this process, the argon gas was kept stable. After cooling to room temperature, the obtained covalent organic framework substrate with loaded ionic metal was sequentially cleaned and dried, and finally reduced under an H2 / Ar gas flow to obtain a group-induced confined framework of CuZn nanoalloys with plasma-injected long-range pores.

7. The method for preparing a group-induced confined framework of CuZn nanoalloys via plasma-impregnated long-range channels as described in claim 6, characterized in that, Based on the addition amount of the covalent organic framework substrate being 50 mg, the total addition amount of copper salt and zinc salt is 10-20 mg; the metal molar ratio of Cu to Zn is 1-2:

1.

8. The method for preparing a group-induced confined framework of CuZn nanoalloys via plasma-impregnated long-range channels as described in claim 7, characterized in that, With the covalent organic framework substrate added at a rate of 50 mg, the total amount of copper and zinc salts added is 15 mg; the metal molar ratio of Cu to Zn is 1~1.2:

1.

9. The method for preparing a group-induced confined framework of CuZn nanoalloys via plasma-impregnated long-range channels as described in claim 6, characterized in that, The plasma excitation chamber and the tube furnace are heated synchronously and continuously, with the temperature set at 300~500℃; the heating time is 2~4 hours.

10. The method for preparing a group-induced confined framework of CuZn nanoalloys via plasma-impregnated long-range channels as described in claim 9, characterized in that, The temperature for simultaneous and continuous heating of the plasma excitation chamber and the tube furnace was set to 400℃, and the heating time was 3 hours.

11. The method for preparing a group-induced confined framework of CuZn nanoalloys via plasma-impregnated long-range channels as described in claim 6, characterized in that, In the H2 / Ar gas flow, the volume fraction of H2 is 5-15%.

12. The method for preparing a group-induced confined framework of CuZn nanoalloys via plasma-impregnated long-range channels as described in claim 11, characterized in that, In the H2 / Ar gas flow, the volume fraction of H2 is 10%.

13. The method for preparing a group-induced confined framework of CuZn nanoalloys via plasma-impregnated long-range channels as described in claim 6, characterized in that, The reduction temperature under H2 / Ar gas flow is 150~300℃; the reduction time is 1~3h.

14. The method for preparing a group-induced confined framework of CuZn nanoalloys via plasma-impregnated long-range channels as described in claim 13, characterized in that, The reduction temperature under H2 / Ar gas flow was 200℃; the reduction time was 2h.

15. The catalytic application of the plasma-impregnated long-range channel group-induced CuZn nanoalloy confined framework as described in any one of claims 1 to 5 in the CO2 reduction reaction to produce C2H4.

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