Copper sulfide nanowire material and preparation method and application thereof

Abstract

The invention provides a copper sulfide nanowire material and a preparation method and application thereof, copper atoms and sulfur atoms on the surface of the copper sulfide nanowire material exist in the form of compounds, and the main component is a Cu2S phase; the preparation method of the copper sulfide nanowire material comprises the steps that nickel chloride hexahydrate, copper acetylacetonate and dimethyl dioctadecyl ammonium chloride serve as raw materials to prepare a Cu nanowire in the presence of oleylamine, and then the Cu nanowire is subjected to vulcanization treatment to obtain the copper sulfide nanowire material. The preparation method is simple and flexible in reaction, the number of nanoparticles on the surface of the copper sulfide nanowire material can be controlled according to needs, and the prepared copper sulfide nanowire material contains copper sulfide nanowires with the diameter of 20-60 nm. The copper sulfide nanowire material can be applied to CO2 electrochemical catalytic reduction or water electrolysis hydrogen production, and the universality is good.

Description

Technical Field

[0001] This invention belongs to the field of metal nanomaterials technology, specifically a copper sulfide nanowire material, its preparation method, and its application. Background Technology

[0002] Copper sulfide nanomaterials are important semiconductor materials widely used in thermocouples, optical recording, filters, solar cells, dry powder coatings, fluorescent materials, and superconductors. Based on their morphology, copper sulfide nanocrystals are classified into various forms such as nanoparticles, nanorods, nanowires, nanotubes, and nanoflowers, and can be synthesized using various methods including hydrothermal synthesis, wet chemical synthesis, template methods, and microwave methods. Researchers in this field have made significant progress in the preparation methods and applications of copper sulfide nanomaterials, for example:

[0003] Patent documents: Patent CN113428889B discloses a layered CuS nanoflower catalyst prepared by doping metal atoms using copper trifluoromethanesulfonate, copper tartrate, or copper gluconate as the copper source and thioaminourea, L-methionine, or 2-thioureapyrimidine as the sulfur source, as a negative electrode material for sodium-ion batteries, exhibiting good electrochemical performance. Patent application CN113264547A discloses a spherical CuS nanoflower catalyst prepared by heating and condensing copper acetylacetonate and n-dodecyl mercaptan under inert gas protection. 1.94 S nanoparticles can effectively absorb ultraviolet or visible light and can be applied in the field of optics. Patent application CN 112279293 A discloses a method for preparing copper sulfide nanorods by simultaneously dissolving sodium sulfide and copper chloride in dilute hydrochloric acid solution, followed by isothermal reflux treatment and a three-step cooling hydrothermal method.

[0004] In the paper, Cu2O seed layer was prepared by rapid oxidation method with hydrogen peroxide after cutting and cleaning of Cu electrode substrate, and then the Cu2O seed layer was rapidly sulfidized into Cu2S in Na2S solution, and then it was used as nucleation site to control the growth of large-size Cu2S nanosheet array by room temperature two-step method to prepare Cu2S-RV (rich in defects) nanosheet array, and then Cu2S-SV (surface defects) and Cu2S-WV (without defects) were prepared through different annealing treatment; and the three kinds of materials with different defect types were used as photoelectrolysis water photoanode, and the performance of the three kinds of materials applied to photoelectrolysis water hydrogen production was studied, and the results showed that the performance of Cu2S-SV was improved relative to Cu2S-WV in AM1.5G and full spectrum range, and the improvement in full spectrum range was more obvious (Research on Sulfide Copper Nanosheet Surface Plasmon Resonance Enhanced Photoelectric Hydrogen Production[D], Ren Kai-xu, 2016-Tianjin University: Materials Science). Zhao Zhe prepared copper sulfide@foam nickel (CuS@NF) catalyst (including copper sulfide nanosheet (CuS-NS) and copper sulfide nanowire (CuS-NW) two kinds of morphology) as CO2 electro-reduction catalyst by growing Cu2O on foam nickel substrate by hydrothermal method; through electrochemical characterization, it is proved that CuS-NS@NF has high CO2 electro-reduction catalytic performance, and has high selectivity for product CH4, and the FE of CH4 reaches 73%±5, and the reaction time can last for 60h; through electrochemical characterization, it is proved that S ion plays an important role in the reaction (Research on Electrochemical Reduction of CO2 Based on Copper Sulfide Nanosheet[D], Zhao Zhe, 2018-Tianjin University of Technology: Electrochemical Reduction of Carbon Dioxide).

[0005] It can be seen that the existing research confirms that the copper sulfide nanomaterial has wide application and good application prospect, but at present, there are few reports on the preparation process of copper sulfide nanomaterial in nanowire form, and the prepared nanomaterial cannot meet the application requirements in multiple aspects. Therefore, it is urgent to develop a simple method to synthesize copper sulfide nanowire with good universality. SUMMARY

[0006] In view of the shortcomings of the prior art, the purpose of the present application is to provide a copper sulfide nanowire material and a preparation method and application thereof. The copper atom and the sulfur atom on the surface of the copper sulfide nanowire material exist in the form of a compound, and the main component is Cu2S phase. There are copper sulfide nanowires with a diameter of 20-60nm in the copper sulfide nanowire material. The copper sulfide nanowire material can be applied in CO2 electrochemical catalytic reduction or water electrolysis hydrogen production, and has good universality. The preparation method of the present application is simple and the reaction is flexible, and the number of nanoparticles on the surface of the copper sulfide nanowire material can be controlled according to needs.

[0007] The application is achieved by the following technical solutions.

[0008] In a first aspect, the application provides a preparation method of copper sulfide nanowire material, which comprises using nickel chloride hexahydrate, copper acetylacetonate and dimethyl dioctadecyl ammonium chloride as raw materials to prepare Cu nanowire in the presence of oleylamine, and then performing sulfidation treatment on the Cu nanowire to obtain copper sulfide nanowire material.

[0009] According to the preparation method provided by the application, the method specifically comprises the following steps:

[0010] (1) copper acetylacetonate, nickel chloride hexahydrate and dimethyl dioctadecyl ammonium chloride are added to a reactor containing oleylamine, and stirring is continuously performed, the reactor is heated to 50-100 DEG C under an inert atmosphere, and is kept at this temperature for 30-60 min; then the temperature is raised to 180-190 DEG C, and is kept at this temperature for 220-270 min to obtain Cu nanowire; and then the temperature is lowered to 30-70 DEG C.

[0011] (2) sulfur powder is first dispersed in oleylamine, and then added to the reactor in step (1), and is stirred uniformly under an inert atmosphere and heated to 90-110 DEG C, and is kept at this temperature for 60-90 min to obtain copper sulfide nanowire.

[0012] According to the preparation method provided by the application, the molar ratio of copper acetylacetonate, nickel chloride hexahydrate and dimethyl dioctadecyl ammonium chloride is (1-2):1:(1-1.5); preferably, the molar ratio of copper acetylacetonate, nickel chloride hexahydrate and dimethyl dioctadecyl ammonium chloride is 2:1:(1-1.5); more preferably, the molar ratio of copper acetylacetonate, nickel chloride hexahydrate and dimethyl dioctadecyl ammonium chloride is 2:1:1.

[0013] According to the preparation method provided by the application, the mass of sulfur powder: the molar mass of nickel chloride hexahydrate = (5-50) g:1 mol; preferably, the mass of sulfur powder: the molar mass of nickel chloride hexahydrate = (10-30) g:1 mol.

[0014] According to the preparation method provided by the application, in step (1), the molar mass of nickel chloride hexahydrate: the volume of oleylamine = 1 mol:(17.5-25) L; preferably, the molar mass of nickel chloride hexahydrate: the volume of oleylamine = 1 mol:(20-25) L.

[0015] According to the preparation method provided by the application, in step (2), the mass of sulfur powder: the volume of oleylamine = (0.4-10) g:1 L; preferably, the mass of sulfur powder: the volume of oleylamine = (1-6) g:1 L.

[0016] According to the preparation method provided in the present application, the step (2) adopts the ultrasonic treatment method to disperse the sulfur powder in the oleylamine. Preferably, the ultrasonic dispersion condition is: ultrasonic treatment for 30-120 min under 160-320 W.

[0017] In some embodiments of the present application, after the heat preservation in the step (2) is finished, the cooling to room temperature is performed, the solid-liquid separation is performed by the centrifugal separation method, and the solid phase is recovered to obtain the copper sulfide nanowires. Preferably, the centrifugal speed is 5000-9000 r, and the centrifugal time is 5-10 min.

[0018] In some embodiments of the present application, the inert gas in the step (1) and the step (2) is selected from Ar or N2.

[0019] In some embodiments of the present application, the preparation method further comprises a step (3): the copper sulfide nanowires obtained in the step (2) are cleaned with an organic solvent and then dried.

[0020] In some embodiments of the present application, the drying temperature in the step (3) is 40-110 ℃, preferably 60-100 ℃; and the drying time is 8-24 h, preferably 10-18 h.

[0021] In some embodiments of the present application, the organic solvent in the step (3) is ethanol and / or n-hexane, preferably the organic solvent is a mixture of ethanol and n-hexane, more preferably, the volume ratio of the ethanol and the n-hexane is (1-2):(1-2).

[0022] In some embodiments of the present application, after the cleaning of the copper sulfide nanowires in the step (3) is finished, the copper sulfide nanowires are first centrifuged to separate the cleaning liquid, and then the copper sulfide nanowires are dried. Preferably, the copper sulfide nanowires are cleaned with the organic solvent for multiple times to remove the oleylamine on the copper sulfide nanowires, and after each cleaning, the copper sulfide nanowires are first centrifuged to separate the cleaning liquid, and then a new round of cleaning is performed. More preferably, the centrifugal speed is 5000-9000 r, and the centrifugal time is 5-10 min.

[0023] In the second aspect, the present application provides a copper sulfide nanowire material prepared by the preparation method in the first aspect.

[0024] According to the copper sulfide nanowire material provided in the present application, the copper atoms and the sulfur atoms on the surface of the copper sulfide nanowire material exist in the form of a compound, and the main component is Cu2S phase.

[0025] In some embodiments of the present application, the nanoparticles on the surface of the copper sulfide nanowire material are uniformly distributed.

[0026] In some embodiments of the present application, the nanoparticles on the surface of the copper sulfide nanowire material are copper sulfide nanoparticles, and the main component is Cu2S phase. Preferably, the copper sulfide nanoparticles uniformly cover the surface of the nanowire.

[0027] According to the present application, the copper sulfide nanowire material contains copper sulfide nanowires with a diameter of 20-60 nm.

[0028] In some embodiments of the present application, the shape and size of the copper sulfide nanowires in the copper sulfide nanowire material are uniform.

[0029] In a third aspect, the present application provides the use of the copper sulfide nanowire material of the second aspect in the electrochemical catalytic reduction of CO2. Preferably, the use includes applying the copper sulfide nanowire material as a catalyst in the process of electrochemical catalytic reduction of CO2.

[0030] In a fourth aspect, the present application provides the use of the copper sulfide nanowire material of the second aspect in the production of hydrogen by electrolysis of water. Preferably, the use includes applying the copper sulfide nanowire material as a catalyst in the process of electrolysis of water to produce hydrogen or applying the copper sulfide nanowire material as an electrode in the process of electrolysis of water to produce hydrogen.

[0031] The present application has the following advantages:

[0032] The present application successfully prepares a copper sulfide nanowire material using an oil amine as an oil phase by a wet chemical method, and the preparation method is simple and the reaction is flexible. By first preparing Cu nanowires and then sulfidizing the Cu nanowires to form a Cu2S phase on the surface of the Cu nanowires, the number of nanoparticles on the surface of the prepared copper sulfide nanowire material is controllable, and the copper sulfide nanowire material contains copper sulfide nanowires with a diameter of 20-60 nm, which has potential application prospects in the field of CO2 electrochemical catalytic reduction technology or the field of hydrogen production by electrolysis of water.

[0033] In the preparation of Cu nanowires, the reactor is first heated to 50-100℃ after the addition of raw materials, and the temperature is maintained for 30-60 min. This allows the raw materials to be fully dispersed and dissolved in the oil amine solution under low temperature stirring conditions, effectively solving the problem of uneven shape of Cu nanowires caused by uneven dispersion of raw materials, and also preventing the formation of Cu nanowires due to the aggregation of a single type of raw material. BRIEF DESCRIPTION OF DRAWINGS

[0034] Figure 1 is a transmission electron microscope image of the copper sulfide nanowire material prepared in application example 1, and from Figure 1 It can be seen that the copper sulfide nanowire material with fine and dense nanoparticles is successfully synthesized in application example 1;

[0035] Figure 2 is a high angle annular dark field imaging image of the copper sulfide nanowire material prepared in Example 1;

[0036] Figure 3 is an elemental analysis image of the copper sulfide nanowire material prepared in Example 1;

[0037] Figure 4 is an X-ray diffraction image of the copper sulfide nanowire material prepared in Example 1;

[0038] Figure 5 is an X-ray photoelectron spectrum of the copper sulfide nanowire material prepared in Example 1;

[0039] Figure 6 is a Cu element X-ray photoelectron spectrum of the copper sulfide nanowire material prepared in Example 1;

[0040] Figure 7 is a S element X-ray photoelectron spectrum of the copper sulfide nanowire material prepared in Example 1;

[0041] Figure 8 is an O element X-ray photoelectron spectrum of the copper sulfide nanowire material prepared in Example 1; Figure 9 is a C element X-ray photoelectron spectrum of the copper sulfide nanowire material prepared in Example 1;

[0042] Figure 10 is a transmission electron microscope image of the copper sulfide nanowire material prepared in Example 2, from Figure 1 and Figure 10 it can be seen from the comparison of

[0043] Figure 11 is a transmission electron microscope image of the copper sulfide nanowire material prepared in Example 3, from Figure 1 and Figure 11 it can be seen from the comparison of

[0044] Figure 12 is a transmission electron microscope image of the copper sulfide nanowire prepared in Example 4, from Figure 12 it can be seen that Example 4 cannot obtain complete one-dimensional copper sulfide nanowires;

[0045] Figure 13 is a transmission electron microscope image of the copper sulfide nanowire prepared in Example 5, from Figure 13 it can be seen that Example 5 can only obtain copper nanowires;

[0046] Figure 14is a transmission electron microscope image of the copper sulfide nanowire prepared in Example 6, from which Figure 14 It can be seen that the nanowire in Example 6 cannot be uniformly covered with copper sulfide nanoparticles;

[0047] Figure 15 is a transmission electron microscope image of the copper sulfide nanowire prepared in Example 7, from which Figure 15 It can be seen that the nanowire in Example 7 cannot be uniformly shaped, and there are a large number of nanoclusters. DETAILED DESCRIPTION

[0048] The following examples further illustrate the technology of the present application. These examples are illustrative and exemplary of the application, and do not limit the scope of the application in any way.

[0049] Example 1

[0050] A method for preparing a copper sulfide nanowire material, comprising the following steps:

[0051] (1) Copper acetylacetonate, nickel chloride hexahydrate, and dimethyl dioctadecyl ammonium chloride are added to a reactor containing oleylamine in a molar ratio of 1:1:1, wherein the molar mass of nickel chloride hexahydrate: the volume of oleylamine = 1 mol: 2 L; continuous stirring is carried out, the reactor is heated to 85°C under an inert atmosphere, and kept for 45 min; then heated to 185°C, kept for 240 min, and then cooled to 50°C.

[0052] (2) Sulfur powder is added to a container containing oleylamine at a ratio of 4 g of sulfur powder dissolved in 1 L of oleylamine, and ultrasonic treatment is carried out at 240 W for 75 min to obtain a sulfur powder solution.

[0053] (3) The sulfur powder solution obtained above is slowly added to the reactor of step (1) at a ratio of sulfur powder mass: molar mass of nickel chloride hexahydrate = 36 g: 1 mol, and then stirred uniformly under N2 atmosphere and heated to 100°C for 60 min. After the reaction is completed, the liquid in the reactor is cooled to room temperature, and then the solid phase is recovered by centrifugal separation to obtain copper sulfide nanowires.

[0054] (4) The copper sulfide nanowires obtained above are washed 3 times with a mixed organic solvent obtained by mixing ethanol and n-hexane in a volume ratio of 1:1, and then the washed copper sulfide nanowires are dried at 75°C for 16 h to obtain a copper sulfide nanowire material.

[0055] Example 2

[0056] A method for preparing a copper sulfide nanowire material, comprising the following steps:

[0057] (1) Copper acetylacetonate, nickel chloride hexahydrate, and dimethyl dioctadecyl ammonium chloride were added to a reactor containing oleylamine in a molar ratio of 2:1:1, wherein the molar mass of nickel chloride hexahydrate:volume of oleylamine = 1 mol:2.5 L; stirring was continuously performed, the reactor was heated to 100°C under an inert atmosphere, and was kept at this temperature for 30 min; then the temperature was raised to 180°C, and was kept at this temperature for 270 min before being cooled to 30°C.

[0058] (2) Sulfur powder was added to a container containing oleylamine in a ratio of 10 g of sulfur powder per 1 L of oleylamine, and was ultrasonically treated at 320 W for 120 min to obtain a sulfur powder solution.

[0059] (3) The sulfur powder solution obtained above was slowly added to the reactor of step (1) in a ratio of the mass of sulfur powder:the molar mass of nickel chloride hexahydrate = 50 g:1 mol, and was uniformly stirred and heated to 110°C under a N2 atmosphere and kept at this temperature for 60 min. After the reaction was completed, the liquid in the reactor was cooled to room temperature, and then the solid phase was recovered by centrifugal separation to obtain copper sulfide nanowires.

[0060] (4) The copper sulfide nanowires obtained above were washed 3 times with a mixed organic solvent obtained by mixing ethanol and n-hexane in a volume ratio of 2:1, and then the washed copper sulfide nanowires were dried at 40°C for 24 h to obtain copper sulfide nanowire materials.

[0061] Example 3

[0062] A method for preparing copper sulfide nanowire materials, comprising the following steps:

[0063] (1) Copper acetylacetonate, nickel chloride hexahydrate, and dimethyl dioctadecyl ammonium chloride were added to a reactor containing oleylamine in a molar ratio of 1:1:1.5, wherein the molar mass of nickel chloride hexahydrate:volume of oleylamine = 1 mol:1.75 L; stirring was continuously performed, the reactor was heated to 50°C under an inert atmosphere, and was kept at this temperature for 60 min; then the temperature was raised to 190°C, and was kept at this temperature for 220 min before being cooled to 70°C.

[0064] (2) Sulfur powder was added to a container containing oleylamine in a ratio of 0.4 g of sulfur powder per 1 L of oleylamine, and was ultrasonically treated at 160 W for 30 min to obtain a sulfur powder solution.

[0065] (3) The sulfur powder solution obtained above was slowly added to the reactor of step (1) in a ratio of the mass of sulfur powder:the molar mass of nickel chloride hexahydrate = 5 g:1 mol, and was uniformly stirred and heated to 90°C under a N2 atmosphere and kept at this temperature for 90 min. After the reaction was completed, the liquid in the reactor was cooled to room temperature, and then the solid phase was recovered by centrifugal separation to obtain copper sulfide nanowires.

[0066] (4) The copper sulfide nanowires obtained above were washed 3 times with a mixed organic solvent obtained by mixing ethanol and n-hexane in a volume ratio of 1:2, and then the washed copper sulfide nanowires were dried at 110°C for 8h to obtain copper sulfide nanowire materials.

[0067] Application Examples

[0068] Application Example 1

[0069] A method for preparing copper sulfide nanowire materials, comprising the following steps:

[0070] (1) Copper acetylacetonate 0.2094g (0.0008mol), nickel chloride hexahydrate 0.0951g (0.0004mol), dimethyldioctadecylammonium chloride 0.3g (0.0005mol) were added into a three-necked flask containing 9mL oleylamine; stirring was continuously conducted, the reactor was heated to 85°C under N2atmosphere and kept for 45min; then it was heated to 185°C and kept for 240min.

[0071] (2) 8mg of sulfur powder was added into a container containing 2mL oleylamine, and ultrasonic treatment was conducted at 240W for 75min to obtain a sulfur powder solution.

[0072] (3) When the temperature of the three-necked flask in step (1) was reduced to 50°C, the sulfur powder solution obtained in step (2) was slowly added into the three-necked flask, which was stirred uniformly and heated to 100°C under N2atmosphere and kept for 60min. After the reaction was completed, the liquid in the three-necked flask was cooled to room temperature, and then the solid phase was recovered by centrifugal separation to obtain copper sulfide nanowires. The centrifugal speed was 8000r, and the time was 7min.

[0073] (4) The copper sulfide nanowires obtained above were washed 3 times with a mixed organic solvent obtained by mixing ethanol and n-hexane in a volume ratio of 1:1, and then the washed copper sulfide nanowires were dried at 75°C for 16h to obtain copper sulfide nanowire materials.

[0074] The obtained copper sulfide nanowire materials were analyzed to obtain a transmission electron microscope image (as shown in FIG. 1), a high-angle annular dark-field imaging image (as shown in FIG. 2), an elemental analysis image (as shown in FIG. 3), an X-ray diffraction pattern (as shown in FIG. 4), an X-ray photoelectron spectrum (as shown in FIG. 5), a Cu element X-ray photoelectron spectrum (as shown in FIG. 6), and a S element X-ray photoelectron spectrum (as shown in FIG. 7). Figure 1 Figure 2 Application Examples Figure 3 Figure 4 Application Example 1 Figure 5 Figure 6 Figure 7 ​​​​X-ray photoelectron spectroscopy (XPS) of O element (as shown in Figure 8 X-ray photoelectron spectroscopy (XPS) of C element (as shown in Figure 9 ).

[0075] Application Example 2

[0076] The application example 1 was repeated, except that the amount of sulfur powder in step (2) was 4 mg.

[0077] The transmission electron microscope image of the copper sulfide nanowire material prepared by the application example is shown in Figure 10 It can be seen from Figure 10 that copper sulfide crystals are distributed in the copper sulfide nanowire material, and the number of copper sulfide crystal particles is significantly less than that of the nanowire material of application example 1.

[0078] Application Example 3

[0079] The application example 1 was repeated, except that the amount of sulfur powder in step (2) was 16 mg.

[0080] The transmission electron microscope image of the copper sulfide nanowire material prepared by the application example is shown in Figure 11 It can be seen from Figure 11 that copper sulfide crystals are distributed in the copper sulfide nanowire material, and the number of copper sulfide crystal particles is significantly more than that of the nanowire material of application example 1.

[0081] Application Example 4

[0082] The application example 1 was repeated, except that the temperature rising and holding in step (1) was as follows: the reactor was heated to 85℃ and held for 45 min; then heated to 150℃ and held for 240 min.

[0083] The transmission electron microscope image of the copper sulfide nanowire material prepared by the application example is shown in Figure 12 It can be seen from Figure 12 that this method cannot obtain complete one-dimensional copper sulfide nanowires.

[0084] Application Example 5

[0085] The application example 1 was repeated, except that the temperature rising and holding in step (1) was as follows: the reactor was heated to 85℃ and held for 45 min; then heated to 200℃ and held for 240 min.

[0086] The transmission electron microscope image of the copper sulfide nanowire material prepared by the application example is shown in Figure 13 It can be seen from Figure 13 that this method can only obtain copper nanowires.

[0087] Application Example 6

[0088] The application example 1 was repeated, with the difference that in step (1) the temperature was raised and maintained as follows: the reactor was raised to 85°C and maintained for 45 min; then raised to 185°C and maintained for 200 min.

[0089] The transmission electron micrograph of the copper sulfide nanowire material prepared by the present application example is shown in Figure 14 From Figure 14 it can be seen that this method cannot obtain nanowires uniformly covered with copper sulfide nanoparticles.

[0090] Application Example 7

[0091] The application example 1 was repeated, with the difference that in step (1) the temperature was raised and maintained as follows: the reactor was directly raised to 185°C and maintained for 240 min.

[0092] The transmission electron micrograph of the copper sulfide nanowire prepared by the present application example is shown in Figure 15 From Figure 15 it can be seen that this method cannot obtain nanowires of uniform shape, with a large number of nanoclusters.

[0093] It should be noted that the above-described examples are only used to explain the present application and do not constitute any limitation on the present application. The examples have described the present application, and it should be understood that the words used therein are descriptive and explanatory words, rather than limiting words. The present application can be modified as specified within the scope of the claims of the present application, and the present application can be revised without departing from the scope and spirit of the present application.

Claims

1. A method for preparing a copper sulfide nanowire material, characterized by, The method comprises the following steps: (1) adding copper acetylacetonate, nickel chloride hexahydrate and dimethyl dioctadecyl ammonium chloride into a reactor containing oleylamine, continuously stirring, heating the reactor to 50-100℃ under an inert atmosphere, and keeping the temperature for 30-60 min; then heating to 180-190℃, keeping the temperature for 220-270 min to obtain Cu nanowires; cooling to 30-70℃; (2) dispersing sulfur powder in oleylamine first, then adding it into the reactor of step (1), stirring uniformly under an inert atmosphere, heating to 90-110℃, and keeping the temperature for 60-90 min to obtain copper sulfide nanowires.

2. The production method according to claim 1, characterized by, The molar ratio of copper acetylacetonate, nickel chloride hexahydrate and dimethyl dioctadecyl ammonium chloride is (1-2):1:(1-1.5); and / or The mass of the sulfur powder: the molar mass of nickel chloride hexahydrate = (5-50) g:1 mol.

3. The production method according to claim 1 or 2, characterized by, In step (1), the molar mass of nickel chloride hexahydrate: the volume of oleylamine = 1 mol:(17.5-25) L; and / or In step (2), the mass of sulfur powder: the volume of oleylamine = (0.4-10) g:1 L; and / or The inert gas in steps (1) and (2) is selected from Ar or N2.

4. The production method according to any one of claims 1 to 3, characterized by, In step (2), the sulfur powder is dispersed in oleylamine by ultrasonic treatment; preferably, the ultrasonic dispersion conditions are: ultrasonic treatment at 160-320 W for 30-120 min.

5. The production method according to any one of claims 1 to 4, characterized by, The preparation method further comprises step (3): cleaning the copper sulfide nanowires obtained in step (2) with an organic solvent and then drying.

6. The production method according to claim 5, wherein The organic solvent in step (3) is ethanol and / or n-hexane, preferably, the organic solvent is a mixture of ethanol and n-hexane, more preferably, the volume ratio of ethanol and n-hexane is (1-2):(1-2); and / or The drying temperature in step (3) is 40-110℃, and the drying time is 8-24 h.

7. The preparation method according to claim 5, characterized in that, After cleaning the copper sulfide nanowires in step (3), the copper sulfide nanowires are first centrifuged to remove water, and then dried; preferably, the copper sulfide nanowires are cleaned multiple times with an organic solvent to remove oleylamine therefrom, and after each cleaning, the copper sulfide nanowires are first centrifuged to remove water, and then cleaned again; more preferably, the centrifugal speed is 5000-9000 r, and the centrifugal time is 5-10 min.

8. A copper sulfide nanowire material prepared by the preparation method of any one of claims 1-7.

9. The copper sulfide nanowire material of claim 8, wherein, The copper atoms and sulfur atoms on the surface of the copper sulfide nanowire material exist in the form of a compound, and the main component is Cu2S phase; and / or The copper sulfide nanowire material contains copper sulfide nanowires with a diameter of 20-60 nm.

10. Use of the copper sulfide nanowire material of claim 8 or 9 in CO2 electrochemical catalytic reduction or electrolysis of water to produce hydrogen.

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