Mutual intercalation autogenous tungsten (molybdenum) copper alloy powder, preparation method and application thereof

Abstract

The present application relates to a kind of mutual embedding autogeny type tungsten (molybdenum) copper alloy powder and its preparation method and application, by controlling organic complex concentration and kind, make positive ion metal salt and negative ion metal group respectively with the hydroxyl oxygen and carboxyl carbon of organic complex form coordination bond composition complex, subsequently with the means of step-by-step heat treatment, can control preparation unique mutual embedding autogeny structure tungsten (molybdenum) copper alloy powder.Based on the technology prepared tungsten (molybdenum) copper alloy powder has significantly enhanced interface interaction, can effectively balance the reduction and oxidation ability of hydrogen evolution (HER) and ethanol oxidation (EOR) active site, improve ethanol assisted hydrogen production catalytic activity, compared with the currently reported ethanol energy-saving hydrogen production catalyst, the stability of this mutual embedding autogeny type powder catalyst under the same current is optimal, has potential application value in electro-synthesis.

Description

Technical Field

[0001] This invention relates to the field of alloy powder materials technology, specifically to an intercalated self-generated tungsten (molybdenum) copper alloy powder, its preparation method, and its application. Background Technology

[0002] Hydrogen is a clean energy carrier with high energy density, playing a vital role in future low-carbon energy systems. However, currently, approximately 50% of the world's hydrogen is produced through steam reforming of methane using natural gas or coalbed methane, a process that generates significant amounts of harmful gases. Therefore, there is an urgent need to develop a new, efficient, and clean hydrogen production process.

[0003] Renewable energy sources such as solar and wind power drive the electrolysis of water to produce hydrogen, enabling energy storage. However, the following problems still exist in the water electrolysis process: (1) 90% of the energy is used for the oxygen evolution reaction (OER); (2) the OER reaction is 4e - The transfer process leads to a high overpotential at the anode's OER, hindering the water electrolysis process. To address this issue, researchers proposed a strategy of small molecule-coupled water splitting, using organic oxidation reactions to replace the sluggish OER process, thereby reducing the voltage of total water splitting. The theoretical voltage of ethanol oxidation coupled with water splitting (EOR) is 0.54 V, significantly lower than the theoretical voltage of total water splitting (1.23 V). Therefore, replacing the OER with EOR can reduce the electrolysis voltage of the water electrolysis hydrogen production system by 56%. In the literature (Nanoscale, 2023, 15, 7765-7771), S and P co-doped Pd metal olefins were synthesized using a solvothermal method and used as a bifunctional electrocatalyst for HER and EOR, achieving a current density of 10 mA cm⁻¹ at 0.88 V. -2 The literature (Int. J. Hydrogen. Energy, 2023, 48, 34244-34254) successfully synthesized tungsten-doped cobalt molybdate nanosheets on porous copper foam using a hydrothermal method, and used them as a catalyst for ethanol-assisted hydrogen production, achieving a 100 mA cm⁻¹ uptake at 1.54 V. -2 Current density, stable operation for 12 hours. Chinese patent (CN114792817A) prepared a Co@Pt core-shell fuel cell catalyst with subsurface Au doping, which exposes platinum atoms on the catalyst surface, improves the utilization rate of platinum, and thus improves the activity of the catalyst.

[0004] The above methods provide insights for the design of energy-saving hydrogen production catalysts, but some problems still need to be addressed: 1) Core-shell structured catalysts exhibit superior bifunctional electrocatalytic activity, but the controllable preparation of intercalated self-generated catalysts derived from core-shell structures remains extremely challenging; 2) Compared with hydrogen production via all-water electrolysis, ethanol-assisted hydrogen production can drive the same current density with a lower voltage, but it is still difficult to achieve high current densities (100 mA cm⁻¹). -2 The challenge of maintaining long-term stability (over 100 hours) of ethanol-assisted hydrogen production remains. Therefore, there is an urgent need to develop novel bifunctional catalysts to solve these key technical challenges. Summary of the Invention

[0005] To address the aforementioned problems, the present invention aims to provide an intercalated self-generated tungsten (molybdenum) copper alloy powder, its preparation method, and its applications.

[0006] To achieve the above objectives, this invention discloses a method for preparing intercalated self-generated tungsten-copper alloy powder, comprising the following steps:

[0007] (1) Prepare a soluble copper salt aqueous solution by adding the organic complex to the soluble copper salt aqueous solution to obtain a mixed solution A;

[0008] Furthermore, the soluble copper salt mentioned in step (1) is one or more of copper nitrate and copper sulfate; the concentration of the aqueous solution of the soluble copper salt is 0.01-2.3 mol / L.

[0009] Furthermore, the organic complex in step (1) is one or more of lactic acid, glycolic acid, and gelatin.

[0010] Furthermore, in step (1), when the organic complex is lactic acid or glycolic acid, the molar ratio of lactic acid or glycolic acid to soluble copper salt is greater than 1:1.

[0011] (2) Prepare a soluble tungsten salt aqueous solution, add the soluble tungsten salt aqueous solution to the mixed solution A, stir continuously and heat to slowly concentrate it to obtain a gel, and then dry the gel in a drying oven to obtain the precursor;

[0012] Furthermore, in step (2), the soluble tungsten salt is one or more of ammonium metatungstate and sodium tungstate, and the concentration of the soluble tungsten salt aqueous solution is 0.01-1.0 mol / L.

[0013] Furthermore, in step (2), the temperature is heated to 30-50°C to slowly concentrate the solution and obtain a gel.

[0014] Furthermore, the volume ratio of the soluble tungsten salt aqueous solution in step (2) to the soluble copper salt aqueous solution in step (1) is 1:1;

[0015] Furthermore, in step (2), the drying temperature of the drying oven is 80-120℃, and the drying time is 2-6h;

[0016] (3) The precursor was calcined in air to obtain tungsten copper composite metal oxide powder;

[0017] Furthermore, in step (3), the calcination of the precursor in air is divided into two stages. First, the precursor is heated from room temperature to the first stage calcination temperature and calcined at the first stage calcination temperature for a period of time. Then, the temperature is raised from the first stage calcination temperature to the second stage calcination temperature and calcined at the second stage calcination temperature for a period of time.

[0018] Furthermore, in step (3), the heating rate of the precursor from room temperature to the first stage calcination temperature is 0.5-6℃ / min, and the heating rate from the first stage calcination temperature to the second stage calcination temperature is 5-13℃ / min; the first stage calcination temperature is 250-420℃, and the calcination time is 2-7h; the second stage calcination temperature is 450-600℃, and the calcination time is 1-5h.

[0019] (4) Tungsten copper composite metal oxide powder was thermally reduced under an argon-hydrogen atmosphere to obtain intercalated self-generated tungsten copper alloy powder.

[0020] Furthermore, the thermal reduction in step (4) is divided into two stages. The tungsten copper composite metal oxide powder is first heated from room temperature to the first stage reduction temperature under an argon-hydrogen atmosphere, and then reduced at the first stage reduction temperature for a period of time. Then, the temperature is raised from the first stage reduction temperature to the second stage reduction temperature, and then reduced at the second stage reduction temperature for a period of time.

[0021] Furthermore, in step (4), the tungsten copper composite metal oxide powder is heated from room temperature to the first stage reduction temperature at a heating rate of 0.2-5℃ / min under an argon-hydrogen atmosphere, and then heated from the first stage reduction temperature to the second stage reduction temperature at a heating rate of 3-6℃ / min.

[0022] Furthermore, in step (4), the first stage reduction temperature is 300-450℃, and the reduction is carried out for 2-5 hours at the first stage reduction temperature; the second stage reduction temperature is 750-850℃, and the reduction is carried out for 1-7 hours at the second stage reduction temperature; the reduction atmosphere is an argon-hydrogen mixture, with hydrogen accounting for 5-15% of the volume.

[0023] The present invention also discloses a method for preparing intercalated self-generated molybdenum-copper alloy powder, which is the same as the method for preparing intercalated self-generated tungsten-copper alloy powder, except that the soluble tungsten salt aqueous solution in step (2) is replaced with a soluble molybdenum salt aqueous solution. The soluble molybdenum salt is one or more of sodium molybdate and ammonium molybdate. The concentration of the soluble molybdenum salt aqueous solution is 0.01-1.0 mol / L. The volume ratio of the soluble molybdenum salt aqueous solution to the soluble copper salt aqueous solution in step (1) is 1:1. Step (3) yields molybdenum-copper composite metal oxide powder. Step (4) involves thermally reducing the molybdenum-copper composite metal oxide powder under an argon-hydrogen atmosphere to obtain intercalated self-generated molybdenum-copper alloy powder.

[0024] The present invention also discloses an intercalated self-generated tungsten-copper alloy powder or an intercalated self-generated molybdenum-copper alloy powder obtained by the above preparation method, and the application of the intercalated self-generated tungsten-copper alloy powder or the intercalated self-generated molybdenum-copper alloy powder in ethanol-assisted energy-saving hydrogen production.

[0025] Compared with the prior art, the present invention has the following beneficial effects:

[0026] (1) In the process of preparing alloy powder using the organic complex precursor method, the positive ion copper and the negative ion tungsten (molybdenum) groups form coordination bonds with the hydroxyl oxygen and carboxyl carbon of the organic complex to form a complex. The oxygen atom provides electrons and the carbon atom provides empty orbitals. The metal cation accepts electrons and forms a coordination bond with the oxygen atom, and the metal anion donates electrons and forms a coordination bond with the carbon atom. During the process of thermal decomposition to remove the organic complex, different metal ions interact with each other and are reduced to form intercalated self-generated tungsten (molybdenum) copper alloy powder.

[0027] (2) This invention mentions the application of intercalated self-generated tungsten-copper alloy powder or intercalated self-generated molybdenum-copper alloy powder in ethanol-assisted water electrolysis for hydrogen production. The unique intercalated self-generated structure can effectively balance the reduction and oxidation capabilities of the HER and EOR active sites, thereby enhancing the catalytic activity of ethanol-assisted hydrogen production. Experimental results show that the current density can reach 100 mA cm⁻¹ at a low voltage of 1.28 V. -2 It operates stably for over 100 hours, maintaining a stability of 87.3%. Compared to currently reported energy-saving ethanol-to-hydrogen catalysts, this intercalated self-generated powder catalyst exhibits the best stability under the same current, demonstrating potential application value in electrosynthesis. Attached Figure Description

[0028] Figure 1 Field emission scanning electron microscope (FESEM) images of the intercalated self-generated tungsten-copper alloy powder prepared in Example 1 at different magnifications;

[0029] Figure 2Field emission scanning electron microscope (FESEM) images of the intercalated self-generated tungsten-copper alloy powder prepared in Example 2 at different magnifications;

[0030] Figure 3 Field emission scanning electron microscope (FESEM) images of the intercalated self-generated tungsten-copper alloy powder prepared in Example 3 at different magnifications;

[0031] Figure 4 Field emission scanning electron microscope (FESEM) images of the intercalated self-generated tungsten-copper alloy powder prepared in Example 4 at different magnifications;

[0032] Figure 5 The X-ray diffraction (XRD) spectra of the intercalated self-generated tungsten-copper alloy powders prepared in Examples 1-4 are shown below.

[0033] Figure 6 The chronocurrent curve of the intercalated self-generated molybdenum-copper alloy powder prepared in Example 5;

[0034] Figure 7 The intercalated self-generated molybdenum-copper alloy powder prepared in Example 6 was subjected to a 1 mol·L⁻¹ concentration. -1 LSV curves in KOH electrolyte;

[0035] Figure 8 The intercalated self-generated molybdenum-copper alloy powder prepared in Example 6, along with the different reported catalysts, achieved 100 mA cm⁻¹ in ethanol-assisted hydrogen production. -2 A bar chart comparing the voltage required for current density. Detailed Implementation

[0036] To better understand the content of this invention, specific embodiments will be used to further illustrate the invention below. The following embodiments are based on the technology of this invention and provide detailed implementation methods and operating steps; however, the scope of protection of this invention is not limited to the following embodiments.

[0037] Example 1:

[0038] (1) Prepare 360 ​​mL of copper nitrate aqueous solution with a concentration of 1.3 mol / L, and add 60 g of lactic acid to the above copper nitrate aqueous solution to obtain mixed solution A;

[0039] (2) Prepare 360 ​​mL of 0.2 mol / L ammonium metatungstate aqueous solution, add the above ammonium metatungstate aqueous solution to mixed solution A, stir continuously and heat to 40°C to slowly concentrate it to obtain gel, and then dry the gel in a drying oven at 80°C for 6 h to obtain the precursor;

[0040] (3) The precursor is calcined in air. First, the precursor is heated from room temperature to 250°C at a heating rate of 5°C / min and calcined at 250°C for 3 hours. Then, the temperature is increased to 500°C at a heating rate of 5°C / min and calcined at 500°C for 3 hours. After calcination, tungsten copper composite metal oxide powder is obtained.

[0041] (4) The tungsten copper composite metal oxide powder was thermally reduced in an argon-hydrogen mixture with a hydrogen volume ratio of 5%. The tungsten copper composite metal oxide powder was heated from room temperature to 350℃ at a heating rate of 5℃ / min and reduced at 350℃ for 3h. Then, the temperature was raised from 350℃ to 750℃ at a heating rate of 5℃ / min and reduced at 750℃ for 6h. After the thermal reduction was completed, intercalated self-generated tungsten copper alloy powder was obtained.

[0042] Example 2:

[0043] (1) Prepare 360 ​​mL of copper nitrate aqueous solution with a concentration of 1.6 mol / L, and add 60 g of glycolic acid to the above copper nitrate aqueous solution to obtain mixed solution A;

[0044] (2) Prepare 360 ​​mL of ammonium metatungstate aqueous solution with a concentration of 0.23 mol / L. Add the above ammonium metatungstate aqueous solution to mixed solution A, stir continuously and heat to 40°C to slowly concentrate it to obtain gel. Then dry the gel in a drying oven at 80°C for 6 h to obtain the precursor.

[0045] (3) The precursor was calcined in air. First, the precursor was heated from room temperature to 250°C at a heating rate of 5°C / min and calcined at 250°C for 3 hours. Then, the temperature was increased to 500°C at a heating rate of 5°C / min and calcined at 500°C for 3 hours. After calcination, tungsten copper composite metal oxide powder was obtained.

[0046] (4) The tungsten copper composite metal oxide powder was thermally reduced in an argon-hydrogen mixture with a hydrogen volume ratio of 5%. The tungsten copper composite metal oxide powder was heated from room temperature to 350℃ at a heating rate of 5℃ / min and reduced at 350℃ for 3h. Then, the temperature was raised from 350℃ to 750℃ at a heating rate of 5℃ / min and reduced at 750℃ for 6h. After the thermal reduction was completed, intercalated self-generated tungsten copper alloy powder was obtained.

[0047] Example 3:

[0048] (1) Prepare 360 ​​mL of copper sulfate aqueous solution with a concentration of 1.0 mol / L, and add 100 g of gelatin to the copper sulfate aqueous solution to obtain mixed solution A;

[0049] (2) Prepare 360 ​​mL of ammonium metatungstate aqueous solution with a concentration of 0.23 mol / L. Add the above ammonium metatungstate aqueous solution to mixed solution A, stir continuously and heat to 40°C to slowly concentrate it to obtain gel. Then dry the gel in a drying oven at 80°C for 6 h to obtain the precursor.

[0050] (3) The precursor was calcined in air. First, the precursor was heated from room temperature to 250°C at a heating rate of 5°C / min and calcined at 250°C for 3 hours. Then, the temperature was increased to 450°C at a heating rate of 5°C / min and calcined at 450°C for 3 hours. After calcination, tungsten copper composite metal oxide powder was obtained.

[0051] (4) The tungsten copper composite metal oxide powder was thermally reduced in an argon-hydrogen mixture with a hydrogen volume ratio of 5%. The tungsten copper composite metal oxide powder was heated from room temperature to 350℃ at a heating rate of 5℃ / min and reduced at 350℃ for 3h. Then, the temperature was raised from 350℃ to 750℃ at a heating rate of 5℃ / min and reduced at 750℃ for 5h. After the thermal reduction was completed, intercalated self-generated tungsten copper alloy powder was obtained.

[0052] Example 4:

[0053] (1) Prepare 360 ​​mL of copper sulfate aqueous solution with a concentration of 2 mol / L, and add 80 g of lactic acid to the above copper sulfate aqueous solution to obtain mixed solution A;

[0054] (2) Prepare 360 ​​mL of sodium tungstate aqueous solution with a concentration of 0.1 mol / L. Add the above sodium tungstate aqueous solution to mixed solution A, stir continuously and heat to 40°C to slowly concentrate it to obtain gel. Then dry the gel in a drying oven at 80°C for 6 h to obtain the precursor.

[0055] (3) The precursor was calcined in air. First, the precursor was heated from room temperature to 250°C at a heating rate of 5°C / min and calcined at 250°C for 3 hours. Then, the temperature was increased to 450°C at a heating rate of 5°C / min and calcined at 450°C for 3 hours. After calcination, tungsten copper composite metal oxide powder was obtained.

[0056] (4) The tungsten copper composite metal oxide powder was thermally reduced in an argon-hydrogen mixture with a hydrogen volume ratio of 5%. The tungsten copper composite metal oxide powder was heated from room temperature to 350℃ at a heating rate of 5℃ / min and reduced at 350℃ for 3h. Then, the temperature was raised from 350℃ to 750℃ at a heating rate of 5℃ / min and reduced at 750℃ for 5h. After the thermal reduction was completed, intercalated self-generated tungsten copper alloy powder was obtained.

[0057] Example 5:

[0058] (1) Prepare 360 ​​mL of copper nitrate aqueous solution with a concentration of 1.8 mol / L, and add 80 g of lactic acid to the above copper nitrate aqueous solution to obtain mixed solution A;

[0059] (2) Prepare 360 ​​mL of sodium molybdate aqueous solution with a concentration of 0.3 mol / L. Add the above sodium molybdate aqueous solution to mixed solution A, stir continuously and heat to 40°C to slowly concentrate it to obtain gel. Then dry the gel in a drying oven at 80°C for 6 h to obtain the precursor.

[0060] (3) The precursor was calcined in air. First, the precursor was heated from room temperature to 250°C at a heating rate of 5°C / min and calcined at 250°C for 3 hours. Then, the temperature was increased to 500°C at a heating rate of 5°C / min and calcined at 500°C for 3 hours. After calcination, molybdenum-copper composite metal oxide powder was obtained.

[0061] (4) The molybdenum-copper composite metal oxide powder was thermally reduced in an argon-hydrogen mixture with a hydrogen volume ratio of 5%. The molybdenum-copper composite metal oxide powder was heated from room temperature to 350℃ at a heating rate of 5℃ / min and reduced at 350℃ for 3h. Then, the temperature was raised from 350℃ to 850℃ at a heating rate of 5℃ / min and reduced at 850℃ for 6h. After the thermal reduction was completed, intercalated self-generated molybdenum-copper alloy powder was obtained.

[0062] Example 6:

[0063] (1) Prepare 360 ​​mL of copper sulfate aqueous solution with a concentration of 2.2 mol / L, and add 90 g of glycolic acid to the above copper sulfate aqueous solution to obtain mixed solution A;

[0064] (2) Prepare 360 ​​mL of 0.35 mol / L ammonium molybdate aqueous solution, add the above ammonium molybdate aqueous solution to mixed solution A, stir continuously and heat to 40°C to slowly concentrate it to obtain gel, and then dry the gel in a drying oven at 80°C for 6 h to obtain the precursor;

[0065] (3) The precursor was calcined in air. First, the precursor was heated from room temperature to 250°C at a heating rate of 5°C / min and calcined at 250°C for 3 hours. Then, the temperature was increased to 550°C at a heating rate of 5°C / min and calcined at 550°C for 3 hours. After calcination, molybdenum-copper composite metal oxide powder was obtained.

[0066] (4) The molybdenum-copper composite metal oxide powder was thermally reduced in an argon-hydrogen mixture with a hydrogen volume ratio of 5%. The molybdenum-copper composite metal oxide powder was heated from room temperature to 350℃ at a heating rate of 5℃ / min and reduced at 350℃ for 3h. Then, the temperature was raised from 350℃ to 850℃ at a heating rate of 5℃ / min and reduced at 850℃ for 6h. After the thermal reduction was completed, intercalated self-generated molybdenum-copper alloy powder was obtained.

[0067] Figure 1 Figures a, b, and c in the figure are FESEM images of the intercalated self-grown tungsten copper alloy powder prepared in Example 1 at different magnifications. It can be seen that the tungsten copper alloy is an intercalated self-grown structure in which tungsten is scattered and grown on the copper surface.

[0068] Figure 2 Figures a, b, and c in the figure are FESEM images of the intercalated self-grown tungsten-copper alloy powder prepared in Example 2 at different magnifications. It can be seen that the tungsten-copper alloy is an intercalated self-grown structure in which tungsten grows uniformly on the copper surface.

[0069] Figure 3 Figures a, b, and c in the figure are FESEM images of the intercalated self-grown tungsten-copper alloy powder prepared in Example 3 at different magnifications. It can be seen that the tungsten-copper alloy is formed by the growth of tungsten on the surface of copper to form an intercalated self-grown structure of tungsten-copper.

[0070] Figure 4 Figures a, b, and c in the figure are FESEM images of the intercalated self-grown tungsten copper alloy powder prepared in Example 4 at different magnifications. It can be seen that the tungsten copper alloy is an intercalated self-grown structure in which tungsten grows sparsely on the copper surface.

[0071] Figure 5 The XRD patterns of the intercalated self-generated tungsten-copper alloy powders prepared in Examples 1-4 are shown. Strong diffraction peaks can be observed in the corresponding patterns. The peak positions are all located at the positions of Cu (PDF#04-0836) and tungsten (PDF#04-0806), which proves that the products prepared in Examples 1-4 are all tungsten-copper alloys.

[0072] Following the method for fabricating the working electrode, the intercalated self-generated molybdenum-copper alloy powder prepared in Example 5 was used as the working electrode for electrochemical testing at 100 mA cm⁻¹. -2 The chronocurrent curve at current density is as follows Figure 6 As shown.

[0073] The working electrode is prepared as follows: Approximately 10 mg of sample is placed in a 10 mL centrifuge tube. Deionized water and anhydrous ethanol are added to the centrifuge tube in a 4:1 ratio to achieve a sample concentration of 2 mg / mL. -1The suspension was sonicated until it was evenly dispersed, and then 250 μL of the evenly dispersed suspension was added dropwise to a 1×1 cm⁻¹ container. 2 The electrode is placed on a nickel foam electrode, and then 25 μL of Nafion aqueous solution is uniformly dispersed on the electrode surface. After drying at 60 °C for 15 min, it can be used as a working electrode for electrochemical testing.

[0074] Electrochemical tests were performed on an electrochemical workstation (CHI-660E, CHI Instruments, Shanghai, China) using a 1 mol L electrolyte. -1 KOH and 1 mol L -1 Ethanol was used as the counter electrode, with a platinum sheet electrode. The sample was used as the working electrode, and the scan rate was 5 mV·s. -1 .

[0075] Figure 6 Stability test results show that at 100mA cm -2 After operating at the initial operating current density for 100 hours, the current density decreased to 87.3 mA cm⁻¹. -2 The retention rate was 87.3%, indicating that it has good stability.

[0076] Following the above method for fabricating the working electrode, the intercalated self-generated molybdenum-copper alloy powder prepared in Example 6 was used as the working electrode for electrochemical testing. The electrochemical test was conducted at 1 mol L... -1 LSV curve in KOH electrolyte, at 1 mol L -1 KOH and 1 mol L -1 The LSV curve in the ethanol electrolyte is as follows: Figure 7 As shown, it reaches 100 mA cm⁻¹ in ethanol-assisted hydrogen production. -2 A bar chart comparing the required operating voltage for current density with that of other materials in the literature is shown below. Figure 8 As shown.

[0077] Figure 7 Performance test results show that at 1 mol L -1 In KOH electrolyte, at 100 mA cm -2 The operating voltage at the specified current density is 1.4V (i.e., the operating voltage for hydrogen production via water electrolysis is 1.4V); at 1 mol L... -1 KOH and 1 mol L -1 In the electrolyte of ethanol, at 100 mA cm -2 The operating voltage at the given current density is 1.28V, indicating that ethanol-assisted hydrogen production has a lower operating voltage compared to water electrolysis for hydrogen production. Figure 8 The bar chart comparison shows that, in the field of ethanol-assisted energy-saving hydrogen production, the intercalated self-generated molybdenum-copper alloy exhibits high performance at 100 mA cm⁻¹. -2The operating voltage at the current density is lower than that of other reported materials, and it exhibits excellent catalytic activity.

[0078] The above description is merely an embodiment of the present invention and is not intended to limit the present invention in any way. The present invention can also have other embodiments based on the above structure and function, which will not be listed hereafter. Therefore, any simple modifications, equivalent changes, and alterations made by those skilled in the art to the above embodiments based on the technical essence of the present invention without departing from the scope of the present invention shall still fall within the scope of the present invention.

Claims

1. A method for preparing intercalated self-generated tungsten-copper alloy powder, characterized in that, Specifically, the following steps are included: (1) Prepare a soluble copper salt aqueous solution by adding an organic complex to the soluble copper salt aqueous solution to obtain a mixed solution A. The organic complex is one or more of lactic acid, glycolic acid, and gelatin. (2) Prepare a soluble tungsten salt aqueous solution, add the soluble tungsten salt aqueous solution to the mixed solution A, stir continuously and heat to slowly concentrate it to obtain a gel, and then dry the gel in a drying oven to obtain the precursor; (3) After calcining the precursor in air, tungsten copper composite metal oxide powder is obtained; (4) Tungsten copper composite metal oxide powder was thermally reduced under an argon-hydrogen atmosphere to obtain intercalated self-generated tungsten copper alloy powder.

2. The method for preparing intercalated self-generated tungsten-copper alloy powder as described in claim 1, characterized in that: The soluble copper salt mentioned in step (1) is one or more of copper nitrate and copper sulfate; the concentration of the aqueous solution of the soluble copper salt is 0.01-2.3 mol / L; when the organic complex is lactic acid or glycolic acid, the molar ratio of lactic acid or glycolic acid to the soluble copper salt is greater than 1:

1.

3. The method for preparing intercalated self-generated tungsten-copper alloy powder as described in claim 1, characterized in that: In step (2), the soluble tungsten salt is one or more of ammonium metatungstate and sodium tungstate. The concentration of the soluble tungsten salt aqueous solution is 0.01-1.0 mol / L, and the volume ratio of the soluble tungsten salt aqueous solution to the soluble copper salt aqueous solution in step (1) is 1:

1. The solution is heated to 30-50℃ and slowly concentrated to obtain a gel. The drying temperature of the drying oven is 80-120℃, and the drying time is 2-6h.

4. The method for preparing intercalated self-generated tungsten-copper alloy powder as described in claim 1, characterized in that: In step (3), the calcination of the precursor in air is divided into two stages. First, the precursor is heated from room temperature to the first stage calcination temperature and calcined at the first stage calcination temperature for a period of time. Then, the temperature is raised from the first stage calcination temperature to the second stage calcination temperature and calcined at the second stage calcination temperature for a period of time.

5. The method for preparing intercalated self-generated tungsten-copper alloy powder as described in claim 1, characterized in that: In step (3), the heating rate of the precursor from room temperature to the first stage calcination temperature is 0.5-6℃ / min, and the heating rate from the first stage calcination temperature to the second stage calcination temperature is 5-13℃ / min; the first stage calcination temperature is 250-420℃, and the calcination time is 2-7 h; the second stage calcination temperature is 450-600℃, and the calcination time is 1-5 h.

6. The method for preparing intercalated self-generated tungsten-copper alloy powder as described in claim 1, characterized in that: The thermal reduction in step (4) is divided into two stages. The tungsten copper composite metal oxide powder is first heated from room temperature to the first stage reduction temperature under an argon-hydrogen atmosphere, and then reduced at the first stage reduction temperature for a period of time. Then, the temperature is raised from the first stage reduction temperature to the second stage reduction temperature, and then reduced at the second stage reduction temperature for a period of time.

7. The method for preparing intercalated self-generated tungsten-copper alloy powder as described in claim 6, characterized in that: In step (4), the tungsten-copper composite metal oxide powder is heated from room temperature to the first-stage reduction temperature at a heating rate of 0.2-5 ℃ / min under an argon-hydrogen atmosphere, and then heated from the first-stage reduction temperature to the second-stage reduction temperature at a heating rate of 3-6 ℃ / min. The first-stage reduction temperature is 300-450 ℃, and the reduction is carried out at the first-stage reduction temperature for 2-5 h. The second-stage reduction temperature is 750-850 ℃, and the reduction is carried out at the second-stage reduction temperature for 1-7 h. The reduction atmosphere is an argon-hydrogen mixture, with hydrogen accounting for 5-15% of the volume.

8. A method for preparing intercalated self-generated molybdenum-copper alloy powder, characterized in that: According to the preparation method of any one of claims 1-7, the soluble tungsten salt aqueous solution in step (2) is replaced with a soluble molybdenum salt aqueous solution. The soluble molybdenum salt is one or more of sodium molybdate and ammonium molybdate. The concentration of the soluble molybdenum salt aqueous solution is 0.01-1.0 mol / L. The volume ratio of the soluble molybdenum salt aqueous solution to the soluble copper salt aqueous solution in step (1) is 1:

1. Step (3) yields molybdenum-copper composite metal oxide powder. Step (4) involves thermally reducing the molybdenum-copper composite metal oxide powder under an argon-hydrogen atmosphere to obtain intercalated self-generated molybdenum-copper alloy powder.

9. The self-generated tungsten-copper alloy powder or the self-generated molybdenum-copper alloy powder prepared by the preparation method according to any one of claims 1 to 8.

10. The application of the intercalated self-generated tungsten-copper alloy powder or the intercalated self-generated molybdenum-copper alloy powder as described in claim 9 in ethanol-assisted energy-saving hydrogen production.

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