Cu-based oxide loaded Cu-based alloy as well as preparation method and application thereof

Abstract

The invention discloses a Cu-based oxide loaded Cu-based alloy and a preparation method and application thereof. Uniformly mixing a Cu source and a second metal source in a solvent, and then centrifuging and drying to obtain a solid precursor; placing the obtained solid precursor in a Joule heating graphite groove, raising the temperature to 600-800 DEG C by using Joule heat generated by pulse discharge under a protective atmosphere, then cooling to room temperature, and circulating heating-cooling for 5-7 times to prepare the Cu-based oxide loaded Cu-based alloy, the method is extremely high in synthesis speed, simple to operate and extremely low in energy consumption, and the obtained material shows excellent catalytic activity and stability in an electro-catalysis carbon dioxide reduction reaction.

Description

Technical Field

[0001] The invention belongs to the technical field of functional material preparation, and particularly relates to a Cu-based oxide-loaded Cu-based alloy and a preparation method and application thereof. Background Art

[0002] The burning of fossil fuels and other human activities emit large amounts of CO 2 In this context, CO 2 It can be used as a resource. Electrocatalytic CO 2 Reduction (CO 2 RR) can use renewable electricity resources (such as solar energy, wind energy and tidal energy) to obtain high value-added chemicals and fuels, realize an artificial closed carbon cycle, and reduce the use of fossil energy such as coal, oil and natural gas to a certain extent; at the same time, it also has the advantages of mild reaction conditions, adjustable selectivity of multiple products, and simple and convenient operation of the device.

[0003] Cu can not only catalyze CO 2 RR produces products containing one carbon, such as CO and formic acid, and is widely considered to be the only 2 Metals that are reduced to hydrocarbons or oxygen-containing compounds with two carbons, but pure Cu has problems such as low product selectivity, poor stability, and high overpotential, while Cu-based alloys can effectively solve these problems to a certain extent. The main reasons are: First, Cu-based alloys can effectively promote CC coupling reactions to produce valuable multi-carbon chemicals such as ethylene. Secondly, by improving the spatial structure and electronic structure of copper-based alloys, the coverage of carbon monoxide (CO) can be significantly increased, and the activation energy barrier for CC bond formation can be reduced, which helps to improve the yield and selectivity of multi-carbon products. Finally, copper-based alloy catalysts show high stability and activity in electrochemical reactions, and can maintain efficient CO over a wide potential range. 2 These advantages make Cu-based oxides supported on Cu-based alloys a promising candidate for CO 2 A promising research direction in the field of RR provides new possibilities for developing efficient and environmentally friendly electrocatalysts.

[0004] The preparation methods of Cu-based oxide-loaded Cu-based alloys mainly include mechanical mixing, ball milling, spray drying, precipitation, and sol-gel. Mechanical mixing: mechanically mix copper with other components, and evenly disperse the components by grinding, stirring, and other means. This method has poor adjustability, complex process, and the performance of the prepared catalyst is average. Ball milling: put copper and other components into a ball mill, and refine and mix the components evenly by ball milling. This method has a long preparation cycle. Spray drying: spray-dry a solution or suspension of copper and other components to obtain a catalyst powder. This method has high energy consumption and poor adjustability. Precipitation: chemically react copper ions with other components to generate a precipitate, and obtain a catalyst powder through filtering, washing, drying, and other steps. This preparation method is complex to operate and has high cost. Sol-gel method: hydrolyze and polymerize the solution of copper and other components to form a sol or gel, and then obtain a catalyst powder through drying, sintering, and other steps. This preparation method is complex to operate and has high cost.

[0005] Therefore, finding a short-term, fast, low-energy synthesis method for Cu-based oxide-loaded Cu-based alloys with simple synthesis process and economic efficiency is of great significance for the development of new and efficient carbon dioxide electroreduction catalysts. Summary of the invention

[0006] The present invention aims to provide a Cu-based oxide-loaded Cu-based alloy and its preparation method and application. The alloy material is synthesized based on Joule heat. This method has a very fast synthesis speed, simple operation and low energy consumption. The prepared Cu-based oxide-loaded Cu-based alloy can be used as a negative electrode material in electrocatalytic CO 2 reduction reaction and exhibits high C 2 H 4 Product selectivity, high catalytic activity and stability.

[0007] The technical solution of the present invention is as follows:

[0008] A method for preparing a Cu-based alloy loaded with a Cu-based oxide, comprising:

[0009] The Cu source and the second metal source are uniformly mixed in a solvent, and then centrifuged and dried (80-120° C.) to obtain a solid precursor; the obtained solid precursor is placed in a Joule-heated graphite groove, heated to 600-800° C. by Joule heat generated by pulse discharge under a protective atmosphere, and then cooled to room temperature, and the heating-cooling cycle is repeated 5-7 times to obtain the Cu-based oxide-loaded Cu-based alloy;

[0010] The preferred feed ratio of Cu source, second metal source, and solvent is 100 mg: 8-15 mg: 6 mL;

[0011] The Cu source is selected from one or more of cupric oxide, copper, and cuprous oxide;

[0012] The metal element in the second metal source is selected from one or more of Ag, Pd, Sn, and Au; the second metal source is specifically, for example, AgNO 3 、PdSO 4 , PdCl 2 , chloropalladium, palladium acetylacetonate, SnCl 2 ·2H 2 O, tetrachloroauric acid trihydrate;

[0013] The solvent is selected from one or more of deionized water, anhydrous methanol, and anhydrous ethanol;

[0014] The protective atmosphere is H 2 atmosphere, Ar atmosphere or 5% (volume fraction) H 2 / Ar atmosphere;

[0015] The voltage of the pulse discharge is 40V, the current is 260-280 amperes, the single discharge time is 5-8s, and the power supply of the pulse discharge is a DC power supply or an AC power supply.

[0016] The invention relates to a Cu-based oxide-loaded Cu-based alloy prepared by the preparation method.

[0017] The Cu-based oxide-loaded Cu-based alloy of the present invention can be used as a negative electrode material for electrocatalytic CO 2 Reduction reaction.

[0018] Compared with the prior art, the present invention has the following beneficial effects:

[0019] The present invention adopts a Joule heat-based ultrafast synthesis method to prepare a Cu-based oxide-loaded Cu-based alloy material. The method has extremely fast synthesis speed, strong operability, short time and low energy consumption.

[0020] The present invention prepares a Cu-based oxide-loaded Cu-based alloy material in a very short time and exhibits high C 2 H 4 Selectivity, good stability and high catalytic activity. BRIEF DESCRIPTION OF THE DRAWINGS

[0021] Figure 1 : Cu-based oxide loaded Cu-based alloy Cu prepared in Example 1.3 Ag 0.9 , CuPd, Cu 5.6 High-resolution transmission electron microscopy (HRTEM) images of Sn; (a) Cu 1.3 Ag 0.9 ; (b) CuPd; (c) Cu 5.6 Sn.

[0022] Figure 2 : Cu-based oxide loaded Cu-based alloy Cu prepared in Example 1.3 Ag 0.9 , CuPd, Cu 5.6 X-ray diffraction (XRD) patterns of Sn; (a) Cu 1.3 Ag 0.9 ; (b) CuPd; (c) Cu 5.6 Sn.

[0023] Figure 3 : Cu-based oxide loaded with Cu prepared in Example 1.3 Ag 0.9 Performance diagram of the alloy in the electrocatalytic carbon dioxide reduction reaction (a); Cu-based oxide supported Cu 1.3 Ag 0.9 Alloy and CuO at different potentials 2 H 4 Performance comparison chart (b); Cu-based oxide loaded Cu 1.3 Ag 0.9 Stability diagram of the alloy at -1.3 V (RHE) potential (c). DETAILED DESCRIPTION

[0024] In order to make the purpose and method of the present invention clearer, the present invention is further described in detail below in conjunction with the embodiments. The examples described here are only used to explain the invention and cannot limit the invention.

[0025] In the following embodiments,

[0026] Joule heating equipment model: JH-3.3-P, Hefei In-situ Technology Co., Ltd., graphite groove size: 3cm*2cm*0.65cm.

[0027] The synthesis method of CuO nanosheets is as follows: 50 mM CuCl 2 ·2H 2 O and 3M NaOH were mixed evenly in deionized water. Then, the mixture was stirred vigorously for 30 min, and then transferred to an autoclave with a polytetrafluoroethylene liner and heated at 100°C for 12 hours. The system was allowed to cool naturally to room temperature, and then the obtained product was centrifuged, washed with deionized water and anhydrous ethanol several times, and then dried in a vacuum oven at 60°C to obtain CuO. (CuO in the present invention is prepared by this method unless otherwise specified)

[0028] Example 1

[0029] This embodiment provides a method for ultrafast synthesis of Cu-based oxides loaded with Cu based on Joule heat. 1.3 Ag 0.9The method comprises the following steps: adding 100 mg of CuO to 6 ml of deionized water and mixing them uniformly by ultrasonic, adding 8 mg of AgNO under vigorous stirring, 3 The mixture was stirred for 5 h, then centrifuged at 9500 rpm for 5 min to obtain a solid precursor, which was then placed in an oven at 80 °C and dried for 6 h.

[0030] 50 mg of the dried sample was placed in a Joule heating device with a pulse discharge voltage of 40 V and a pulse discharge current of 260 amperes. The temperature was rapidly raised to 600 °C in an argon atmosphere and then lowered to room temperature. The rapid heating-cooling cycle was repeated 6 times to obtain Cu-based oxide loaded Cu. 1.3 Ag 0.9 Alloy samples.

[0031] Figure 1 (a) shows Cu 1.3 Ag 0.9 The microstructure of the sample shows the presence of tiny particles. Figure 2 The diffraction peaks in (a) contain Ag and Cu diffraction peaks, and the component content is determined to further determine the Cu 1.3 Ag 0.9 existence; Figure 3 (a)-(c) show Cu 1.3 Ag 0.9 Performance in electrocatalytic carbon dioxide reduction reaction (a); Cu-based oxides loaded with Cu 1.3 Ag 0.9 Alloy and CuO at different potentials 2 H 4 Performance comparison chart (b); Cu-based oxide loaded Cu 1.3 Ag 0.9 Stability of the alloy at a potential of -1.3 V (RHE) (c).

[0032] Example 2

[0033] This embodiment provides a method for ultrafast synthesis of Cu-based oxides loaded with Cu based on Joule heat. 1.3 Ag 0.9 The method comprises the following steps: adding 100 mg of CuO to a mixed solution of 6 ml of deionized water and anhydrous ethanol (deionized water: anhydrous ethanol = 1:1) and mixing by ultrasonication; adding 8 mg of AgNO 3 The mixture was stirred for 5 h, then centrifuged at 9500 rpm for 5 min to obtain a solid precursor, which was then placed in an oven at 80 °C and dried for 6 h.

[0034] 50 mg of the dried sample was placed in a Joule heating device with a pulse discharge voltage of 40 V and a pulse discharge current of 270 amperes. The temperature was rapidly raised to 700 °C in an argon atmosphere and then lowered to room temperature. The rapid heating-cooling cycle was repeated 7 times to obtain Cu-based oxide loaded Cu. 1.3 Ag 0.9 Alloy samples.

[0035] Example 3

[0036] This embodiment provides a method for ultrafast synthesis of Cu-based oxides loaded with Cu based on Joule heat. 1.3 Ag 0.9 The method comprises the following steps: adding 100 mg of CuO to a mixed solution of 6 ml of deionized water and anhydrous methanol (deionized water: anhydrous methanol = 1:1) and mixing them uniformly by ultrasonication; adding 10 mg of AgNO 3 The mixture was stirred for 5 h, then centrifuged at 9500 rpm for 5 min to obtain a solid precursor, which was then placed in an oven at 80 °C and dried for 6 h.

[0037] 50 mg of the dried sample was placed in a Joule heating device with a pulse discharge voltage of 40 V and a pulse discharge current of 270 amperes. The temperature was rapidly raised to 700 °C in an argon atmosphere and then lowered to room temperature. The rapid heating-cooling cycle was repeated 7 times to obtain Cu-based oxide loaded Cu. 1.3 Ag 0.9 Alloy samples.

[0038] Example 4

[0039] This embodiment provides a method for ultrafast synthesis of Cu-based oxides loaded with Cu based on Joule heat. 1.3 Ag 0.9 The method comprises the following steps: adding 100 mg of CuO to a mixed solution of 6 ml of deionized water and anhydrous ethanol (deionized water: anhydrous ethanol = 1:1) and mixing them uniformly by ultrasonication; adding 12 mg of AgNO 3 The mixture was stirred for 5 h, then centrifuged at 9500 rpm for 5 min to obtain a solid precursor, which was then placed in an oven at 80 °C and dried for 6 h.

[0040] 50 mg of the dried sample was placed in a Joule heating device, the pulse discharge voltage was 40 V, the pulse discharge current was 280 amperes, and the temperature was rapidly raised to 800 ° C in a 5% hydrogen / argon atmosphere, and then cooled to room temperature; the rapid heating-cooling cycle process was repeated 6 times to obtain Cu-based oxide-loaded Cu. 1.3 Ag 0.9 Alloy samples.

[0041] Example 5

[0042] This embodiment provides a method for ultrafast synthesis of Cu-based oxides loaded with Cu based on Joule heat. 1.3 Ag 0.9 The method comprises the following steps: adding 100 mg of commercial CuO to a mixed solution of 6 ml of deionized water and anhydrous ethanol (deionized water: anhydrous ethanol = 1:1) and mixing by ultrasonication; adding 12 mg of AgNO 3 The mixture was stirred for 5 h, then centrifuged at 9500 rpm for 5 min to obtain a solid precursor, which was then placed in an oven at 80 °C and dried for 6 h.

[0043] 50 mg of the dried sample was placed in a Joule heating device, the pulse discharge voltage was 40 V, the pulse discharge current was 270 amperes, and the temperature was rapidly raised to 700 ° C in a 5% hydrogen / argon atmosphere, and then cooled to room temperature; the rapid heating-cooling cycle process was repeated 7 times to obtain Cu-based oxide-loaded Cu. 1.3 Ag 0.9 Alloy samples.

[0044] Example 6

[0045] This embodiment provides a method for ultrafast synthesis of Cu-based oxide-loaded CuPd alloy based on Joule heat, comprising the following steps: adding 100 mg of CuO to a mixed solution of 6 ml of deionized water and anhydrous ethanol (deionized water: anhydrous ethanol = 1:1) and mixing by ultrasonication; adding 8 mg of PdSO 4 The mixture was stirred for 5 h and then centrifuged at 9500 rpm for 5 min to obtain a solid precursor, which was then placed in an oven at 100 °C and dried for 6 h.

[0046] Take 50 mg of the dried sample and put it into a Joule heating device. The pulse discharge voltage is 40 V, the pulse discharge current is 260 amperes, and the temperature is rapidly raised to 600°C in an argon atmosphere, and then lowered to room temperature. The rapid heating-cooling cycle process is repeated 7 times to obtain a sample of Cu-based oxide loaded CuPd alloy.

[0047] Figure 1 (b) shows the microstructure of CuPd, where the presence of larger particles can be observed; Figure 2 The diffraction peaks in (b) contain CuPd diffraction peaks, which further confirm the existence of Cu-based oxide-supported CuPd alloy.

[0048] Example 7

[0049] This embodiment provides a method for ultrafast synthesis of Cu-based oxide-loaded CuPd alloy based on Joule heat, comprising the following steps: adding 100 mg of CuO to a mixed solution of 6 ml of deionized water and anhydrous ethanol (deionized water: anhydrous ethanol = 1:1) and mixing by ultrasonication; adding 10 mg of PdSO 4 The mixture was stirred for 5 h and then centrifuged at 9500 rpm for 5 min to obtain a solid precursor, which was then placed in an oven at 100 °C and dried for 6 h.

[0050] Take 50 mg of the dried sample and put it into a Joule heating device. The pulse discharge voltage is 40 V, the pulse discharge current is 280 amperes, and the temperature is rapidly raised to 800°C in an argon atmosphere, and then lowered to room temperature. The rapid heating-cooling cycle process is repeated 6 times to obtain a sample of Cu-based oxide-loaded CuPd alloy.

[0051] Example 8

[0052] This embodiment provides a method for ultrafast synthesis of Cu-based oxide-loaded CuPd alloy based on Joule heat, comprising the following steps: adding 100 mg of CuO to 6 ml of deionized water and mixing them uniformly by ultrasonication; adding 15 mg of PdSO under vigorous stirring; 4 The mixture was stirred for 5 h and then centrifuged at 9500 rpm for 5 min to obtain a solid precursor, which was then placed in an oven at 100 °C and dried for 6 h.

[0053] Take 50 mg of the dried sample and put it into a Joule heating device. The pulse discharge voltage is 40 V, the pulse discharge current is 270 amperes, and the temperature is rapidly raised to 700°C in a 5% hydrogen / argon atmosphere, and then lowered to room temperature. The rapid heating-cooling cycle process is repeated 6 times to obtain a sample of Cu-based oxide-loaded CuPd alloy.

[0054] Example 9

[0055] This embodiment provides a method for ultrafast synthesis of Cu-based oxide-loaded CuPd alloy based on Joule heat, comprising the following steps: adding 100 mg of CuO to 6 ml of anhydrous ethanol and mixing them uniformly by ultrasonication; adding 15 mg of PdCl under vigorous stirring; 2 The mixture was stirred for 5 h and then centrifuged at 9500 rpm for 5 min to obtain a solid precursor, which was then placed in an oven at 100 °C and dried for 6 h.

[0056] 50 mg of the dried sample was placed in a Joule heating device with a pulse discharge voltage of 40 V and a pulse discharge current of 270 amperes. The temperature was rapidly raised to 700°C in an argon atmosphere and then lowered to room temperature. The rapid heating-cooling cycle was repeated 6 times to obtain a sample of Cu-based oxide-loaded CuPd alloy.

[0057] Example 10

[0058] This embodiment provides a method for ultrafast synthesis of Cu-based oxides loaded with Cu based on Joule heat. 5.6 The method comprises the following steps: adding 100 mg of CuO to a mixed solution of 6 ml of deionized water and anhydrous ethanol (deionized water: anhydrous ethanol = 1:1) and mixing them uniformly by ultrasonication; adding 8 mg of SnCl 2 ·2H 2 O and stirred for 5 h, then centrifuged at 9500 rpm for 5 min to obtain a solid precursor, and finally moved into a 100 °C oven to dry for 6 h.

[0059] 50 mg of the dried sample was placed in a Joule heating device with a pulse discharge voltage of 40 V and a pulse discharge current of 280 amperes. The temperature was rapidly raised to 800 °C in an argon atmosphere and then lowered to room temperature. The rapid heating-cooling cycle was repeated 7 times to obtain Cu-based oxide loaded Cu. 5.6 Samples of Sn alloy.

[0060] Figure 1 (c) shows Cu 5.6 In the microstructure of Sn, the presence of smaller particles can be observed; Figure 2 The diffraction peak in (c) contains Cu 5.6 Sn diffraction peaks further confirmed that Cu-based oxides loaded Cu 5.6 The presence of Sn alloy.

[0061] Embodiment 11

[0062] This embodiment provides a method for ultrafast synthesis of Cu-based oxides loaded with Cu based on Joule heat. 5.6 The method comprises the following steps: adding 100 mg of CuO to 6 ml of deionized water and mixing them uniformly by ultrasonic, and adding 12 mg of SnCl under vigorous stirring. 2 ·2H 2 O and stirred for 5 h, then centrifuged at 9500 rpm for 5 min to obtain a solid precursor, and finally moved into a 120 °C oven to dry for 6 h.

[0063] 50 mg of the dried sample was placed in a Joule heating device with a pulse discharge voltage of 40 V and a pulse discharge current of 270 amperes. The temperature was rapidly raised to 700 °C in an argon atmosphere and then lowered to room temperature. The rapid heating-cooling cycle was repeated 7 times to obtain Cu-based oxide loaded Cu. 5.6 Samples of Sn alloy.

[0064] Example 12

[0065] This embodiment provides a method for ultrafast synthesis of Cu-based oxides loaded with Cu based on Joule heat. 5.6 The method comprises the following steps: adding 100 mg of CuO to 6 mL of deionized water and mixing them evenly with ultrasonic, adding 15 mg of SnCl under vigorous stirring, 2 ·2H 2 O and stirred for 5 h, then centrifuged at 9500 rpm for 5 min to obtain a solid precursor, and finally moved into a 120 °C oven to dry for 6 h.

[0066] 50 mg of the dried sample was placed in a Joule heating device, the pulse discharge voltage was 40 V, the pulse discharge current was 260 amperes, and the temperature was rapidly raised to 600 ° C in a 5% hydrogen / argon atmosphere, and then cooled to room temperature; the rapid heating-cooling cycle process was repeated 6 times to obtain Cu-based oxide-loaded Cu. 5.6 Samples of Sn alloy.

[0067] Performance Testing

[0068] Electrocatalytic measurements were performed in an H-type cell with a three-electrode system using an electrochemical workstation (DH7003, Donghua Electrochemical Workstation). The catalyst ink was drop-coated on hydrophobic carbon paper as the working electrode, Pt mesh as the counter electrode, and Ag / AgCl (saturated KCl) electrode as the reference electrode. A 0.1M K 2 SO 4 The H-type electrolytic cell contains 40 mL of electrolyte in each compartment, and the electrolyte in each compartment is CO 2 Bubble for at least 30 minutes to generate CO 2 The working electrode and the reference electrode were placed in the cathode chamber, and the counter electrode was placed in the anode chamber. The two chambers were separated by a Nafion211 proton exchange membrane (purchased from Suzhou Shengernuo Technology Co., Ltd.) to avoid CO 2 Reoxidation of RR generated products. The test voltage range is -0.9V to -1.5V, and all measured potentials are converted to reversible hydrogen electrode. Stability test is carried out at -1.3V (RHE).

[0069] The preparation method of the catalyst ink is as follows: 2 mg of sample powder (i.e. the above-mentioned Cu-based oxide loaded Cu-based alloy sample) and 10 μL of Nafion solution (purchased from Aladdin Reagent (Shanghai) Co., Ltd., specification ~5% in a mixture of lower aliphatic alcohols and water) are ultrasonically dispersed in 250 μL of anhydrous ethanol for 30 minutes. Then 250 μL of the catalyst ink is dripped on a 1×1 cm hydrophobic carbon paper (hydrophobic carbon paper purchased from Suzhou Shengernuo Technology Co., Ltd.).

[0070] Depend on Figure 3 It can be seen that the Cu-based oxide prepared in Example 1 supports Cu 1.3 Ag 0.9 The alloy electrocatalyst exhibits stronger CO than CuO 2 RR reduction performance, Cu-based oxides loaded with Cu 1.3 Ag 0.9 The presence of alloy can significantly increase C 2 H 4 The selectivity of the chelator was good and the activity was maintained at a high level in the stability test for up to 15 h.

[0071] In summary, the present invention proposes a method for ultrafast synthesis of Cu-based oxide-loaded Cu-based alloy based on Joule heat. The preparation method is simple and fast, easy to operate, and has low energy consumption. Cu-based oxide-loaded Cu-based alloy can be prepared in a short time, and exhibits excellent electrocatalytic activity in the electrocatalytic reduction reaction of carbon dioxide.

[0072] The above is only a preferred specific implementation manner of the present invention, and the protection scope of the present invention is not limited thereto. Any simple change or equivalent replacement of the technical solution that can be obviously obtained by any technician familiar with the technical field within the technical scope disclosed in the present invention falls within the protection scope of the present invention.

Claims

1. A method for preparing a Cu-based alloy loaded with a Cu-based oxide, characterized in that: The method comprises: The Cu source and the second metal source are mixed uniformly in a solvent, and then centrifuged and dried to obtain a solid precursor; the obtained solid precursor is placed in a Joule-heated graphite groove, and the Joule heat generated by pulse discharge is used to heat the solid precursor to 600-800° C. in a protective atmosphere, and then cooled to room temperature, and the heating-cooling cycle is repeated 5-7 times to obtain the Cu-based oxide-loaded Cu-based alloy; The Cu source is selected from one or more of cupric oxide, copper, and cuprous oxide; The metal element in the second metal source is selected from one or more of Ag, Pd, Sn and Au.

2. The method for preparing a Cu-based alloy supported by a Cu-based oxide according to claim 1, characterized in that: The second metal source is selected from one or more of: AgNO3, PdSO4, PdCl2, chloropalladate, palladium acetylacetonate, SnCl2·2H2O, and tetrachloroauric acid trihydrate.

3. The method for preparing a Cu-based alloy supported by a Cu-based oxide according to claim 1, characterized in that: The feed ratio of Cu source, second metal source and solvent is 100 mg:8-15 mg:6 mL.

4. The method for preparing a Cu-based alloy supported by a Cu-based oxide according to claim 1, characterized in that: The solvent is selected from one or more of deionized water, anhydrous methanol and anhydrous ethanol.

5. The method for preparing a Cu-based alloy supported by a Cu-based oxide according to claim 1, characterized in that: The protective atmosphere is H2 atmosphere, Ar atmosphere or 5% H2 / Ar atmosphere.

6. The method for preparing a Cu-based alloy supported by a Cu-based oxide according to claim 1, characterized in that: The voltage of the pulse discharge is 40V, the current is 260-280 amperes, the single discharge time is 5-8s, and the power supply of the pulse discharge is a DC power supply or an AC power supply.

7. The Cu-based oxide-loaded Cu-based alloy obtained by the preparation method according to any one of claims 1 to 6.

8. Use of the Cu-based oxide loaded Cu-based alloy as claimed in claim 7 as a negative electrode material in an electrocatalytic CO2 reduction reaction.

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