CN111575764A - Composite nickel-tungsten-copper alloy, preparation method and application thereof - Google Patents
Composite nickel-tungsten-copper alloy, preparation method and application thereof Download PDFInfo
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- CN111575764A CN111575764A CN202010424976.7A CN202010424976A CN111575764A CN 111575764 A CN111575764 A CN 111575764A CN 202010424976 A CN202010424976 A CN 202010424976A CN 111575764 A CN111575764 A CN 111575764A
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Abstract
The invention provides a preparation method of a composite nickel-tungsten-copper alloy, which comprises the steps of firstly, carrying out anodic oxidation on foam copper in a sodium hydroxide solution to obtain a copper hydroxide nanowire array/foam copper compound, carrying out hydrothermal reaction on the compound, nickel salt, tungsten salt and water, drying in vacuum to obtain an initial composite nickel-tungsten-copper alloy precursor, and finally carrying out heat treatment on the initial composite nickel-tungsten-copper alloy precursor to obtain the composite nickel-tungsten-copper alloy; the composite nickel-tungsten-copper alloy consists of a foam copper substrate and a nickel-tungsten-copper alloy which is loaded on the foam copper substrate and is distributed in a hollow nano tube shape, can be directly used as an alkaline hydrogen oxidation reaction catalyst, and has higher catalytic activity. Experiments show that the inventionThe prepared composite nickel-tungsten-copper alloy has excellent alkaline hydrogen oxidation reaction electrocatalytic performance, and the platform current of the composite nickel-tungsten-copper alloy can reach nearly 20mA/cm2。
Description
Technical Field
The invention relates to the technical field of alkaline hydrogen oxidation reaction, in particular to a composite nickel-tungsten-copper alloy, a preparation method and application thereof.
Background
In recent years, the ever-increasing large consumption of fossil fuels has caused serious air pollution, greenhouse effect, and many other environmental problems; there is an urgent need to find new clean energy sources that can be sustainably developed to meet these challenges.
Among the existing new energy technologies, hydrogen energy has received much attention due to its widespread use in proton exchange membrane fuel cells. Although the hydrogen oxidation reaction under acidic conditions is extremely fast and requires only small platinum group metal loadings, the major limitation in proton exchange membrane fuel cells comes from the oxygen reduction reaction, which still requires high platinum metal loadings due to lower activity, which greatly limits the development of this technology. However, the advent of anion exchange membrane fuel cells has brought to this area a transition; because the current oxygen reduction catalysts have been almost replaced by non-noble metal catalysts in alkaline media, this greatly reduces the cost of use, but with a concomitant substantial reduction in the activity of the anodic hydrogen oxidation reaction. Recent studies have reported that non-noble metal nickel-based catalysts are effective in catalyzing hydrogen oxidation reactions, but there is still some gap in performance from noble metal catalysts.
A series of progresses of catalytic hydrogen oxidation reaction of a non-noble metal catalyst in an alkaline environment have been achieved, and mainly focus on a nickel-based catalyst, including a nickel-based alloy, a nickel/nickel oxide heterojunction and the like, wherein element doping is used for regulating and controlling hydrogen bonding energy on the surface of nickel, and the strategy is regarded as a strategy capable of effectively improving the activity of the alkaline hydrogen oxidation reaction. However, the catalytic activity of the nickel-based catalyst for catalyzing the hydrogen oxidation reaction is still not high enough so far, and the nickel-based catalyst cannot be compared with a noble metal catalyst such as a platinum-based catalyst, thereby limiting the wide application.
Disclosure of Invention
The invention aims to provide a preparation method of a composite nickel-tungsten-copper alloy, and the composite nickel-tungsten-copper alloy prepared by the method has higher electrocatalytic performance in an electrocatalytic alkaline hydrogen oxidation reaction.
In view of this, the present application provides a method for preparing a composite nickel-tungsten-copper alloy, including the following steps:
A) cleaning the foamy copper and then carrying out anodic oxidation in a sodium hydroxide solution to obtain a copper hydroxide nanowire array/foamy copper compound;
B) carrying out hydrothermal reaction on the copper hydroxide nanowire array/foam copper compound, nickel salt, tungsten salt and water, and carrying out vacuum drying to obtain an initial composite nickel-tungsten-copper alloy precursor;
C) and carrying out heat treatment on the initial composite nickel-tungsten-copper alloy precursor to obtain the composite nickel-tungsten-copper alloy.
Preferably, the concentration of the sodium hydroxide solution is 1-2 mol/L.
Preferably, the current density of the anodic oxidation is constant current of 10-20 mA/cm2The time is 10-30 min.
Preferably, the atomic ratio of nickel to tungsten in the nickel salt and the tungsten salt is (2-5): 1.
preferably, the temperature of the hydrothermal reaction is 120-150 ℃ and the time is 6-12 h.
Preferably, the heat treatment is at 5% H2The reaction is carried out in an Ar atmosphere at the temperature of 300-600 ℃ for 0.5-2 h.
Preferably, the cleaning is ultrasonic cleaning in dilute hydrochloric acid, ethanol and deionized water in sequence.
The application also provides the composite nickel-tungsten-copper alloy prepared by the preparation method, which consists of a foam copper substrate and the nickel-tungsten-copper alloy which is loaded on the foam copper substrate and is distributed in a hollow nano tube shape.
The application also provides the composite nickel-tungsten-copper alloy prepared by the preparation method or the application of the composite nickel-tungsten-copper alloy in electrocatalytic alkaline hydrogen oxidation.
The application provides a preparation method of a composite nickel-tungsten-copper alloy, which comprises the steps of firstly, carrying out anodic oxidation on foam copper in a sodium hydroxide solution to obtain a copper hydroxide nanowire array/foam copper compound, carrying out hydrothermal reaction on the compound, nickel salt, tungsten salt and water, drying in vacuum to obtain an initial composite nickel-tungsten-copper alloy precursor, and finally carrying out thermal treatment on the initial composite nickel-tungsten-copper alloy precursor to obtain the composite nickel-tungsten-copper alloy; the composite nickel-tungsten-copper alloy consists of a foam copper substrate and a nickel-tungsten-copper alloy which is loaded on the foam copper substrate and is distributed in a hollow nano tube shape, can be directly used as an alkaline hydrogen oxidation reaction catalyst, and has higher catalytic activity; further, in the above-mentioned case,the shape of alloy particles in the composite nickel-tungsten-copper alloy is adjusted by adjusting the proportion of reactants and the heat treatment temperature and time. Experiments show that the composite nickel-tungsten-copper alloy prepared by the invention has excellent alkaline hydrogen oxidation reaction electrocatalytic performance, and the platform current of the composite nickel-tungsten-copper alloy can reach nearly 20mA/cm2。
Drawings
FIG. 1 is a scanning electron micrograph of a composite nickel-tungsten-copper alloy obtained in example 1 of the present invention;
FIG. 2 is an X-ray crystal diffraction pattern of the composite nickel-tungsten-copper alloy obtained in examples 1 to 4 of the present invention;
FIG. 3 is a polarization curve of the composite nickel-tungsten-copper alloy obtained in examples 1 to 4 of the present invention and the nickel-copper alloy obtained in comparative example 1 at 0 to 0.3V (vs. RHE);
FIG. 4 is a polarization curve diagram of the composite nickel-tungsten-copper alloy obtained in examples 1, 5 and 7 of the present invention at 0-0.3V (vs. RHE);
FIG. 5 is a polarization curve of the composite nickel-tungsten-copper alloy obtained in examples 1, 8 to 10 of the present invention at 0 to 0.3V (vs. RHE);
FIG. 6 is a scanning electron micrograph of the composite nickel-tungsten-copper alloy obtained in example 2 of the present invention;
FIG. 7 is a scanning electron micrograph of a composite nickel-tungsten-copper alloy obtained in example 3 of the present invention;
FIG. 8 is a scanning electron micrograph of copper foam according to example 4 of the present invention;
FIG. 9 is a SEM photograph of copper hydroxide nanowire array/foam copper in example 4 of the present invention;
FIG. 10 is a scanning electron micrograph of an initial composite nickel-tungsten-copper alloy precursor according to example 4 of the present invention;
FIG. 11 is a SEM photograph of the composite Ni-W-Cu alloy obtained in example 4 of the present invention;
FIG. 12 is a TEM image of the composite Ni-W-Cu alloy obtained in example 4 of the present invention;
FIG. 13 is a SEM photograph of a composite Ni-W-Cu alloy obtained in example 5 of the present invention;
FIG. 14 is a SEM photograph of a composite Ni-W-Cu alloy obtained in example 6 of the present invention;
FIG. 15 is a SEM photograph of a composite Ni-W-Cu alloy obtained in example 7 of the present invention;
FIG. 16 is a SEM photograph of a composite Ni-W-Cu alloy obtained in example 8 of the present invention;
FIG. 17 is a SEM photograph of a composite Ni-W-Cu alloy obtained in example 9 of the present invention;
FIG. 18 is a SEM photograph of a composite Ni-W-Cu alloy obtained in example 10 of the present invention;
FIG. 19 is a scanning electron micrograph of a composite nickel-tungsten-copper alloy obtained in comparative example 1 of the present invention.
Detailed Description
For a further understanding of the invention, reference will now be made to the preferred embodiments of the invention by way of example, and it is to be understood that the description is intended to further illustrate features and advantages of the invention, and not to limit the scope of the claims.
In view of the problem of low reaction activity of non-noble metal catalysts in the electrocatalytic alkaline hydrogen oxidation reaction, the application provides a composite nickel-tungsten-copper alloy which actually consists of copper foam and nickel-tungsten-copper alloy which is supported on a copper foam substrate and distributed in a hollow nano tube shape, wherein the nickel-tungsten-copper is nano alloy particles which have large specific surface area, thereby having higher electrocatalytic performance. Specifically, the embodiment of the invention discloses a preparation method of a composite nickel-tungsten-copper alloy, which comprises the following steps:
A) cleaning the foamy copper and then carrying out anodic oxidation in a sodium hydroxide solution to obtain a copper hydroxide nanowire array/foamy copper compound;
B) carrying out hydrothermal reaction on the copper hydroxide nanowire array/foam copper compound, nickel salt, tungsten salt and water, and carrying out vacuum drying to obtain an initial composite nickel-tungsten-copper alloy precursor;
C) and carrying out heat treatment on the initial composite nickel-tungsten-copper alloy precursor to obtain the composite nickel-tungsten-copper alloy.
In the process of preparing the composite nickel-tungsten-copper alloy, the copper hydroxide nanowire array/foam copper composite is firstly prepared, which is the key for preparing the composite nickel-tungsten-copper alloy. Specifically, the copper foam is cleaned and then anodized in a sodium hydroxide solution. The cleaning is to ultrasonically clean the foam copper in dilute hydrochloric acid, ethanol and deionized water for several times in sequence to remove surface impurities; the copper foam is well known to those skilled in the art, and there is no particular limitation in this application. After cleaning, the copper foam is subjected to anodic oxidation in a sodium hydroxide solution, during the anodic oxidation, the surface part of the copper foam is converted to be attached to a copper foam substrate in a copper hydroxide nano array, and most of the remaining copper foam is still in the form of the copper foam substrate. The copper hydroxide nanowire array/foam copper compound can be obtained only in a sodium hydroxide solution, but cannot be obtained in other alkaline solutions such as potassium hydroxide. The concentration of the sodium hydroxide solution is 1-2 mol/L, and the current density of anodic oxidation is constant current of 10-20 mA/cm2The time is 10-30 min; more specifically, the concentration of the sodium hydroxide solution is 1mol/L, and the constant current is 15mA/cm2The time is 20 min.
After the copper hydroxide nanowire array/foam copper compound is obtained, preferably washing, drying, carrying out hydrothermal reaction on the copper hydroxide nanowire array/foam copper compound, nickel salt, tungsten salt and water, and carrying out vacuum drying to obtain an initial composite nickel-tungsten-copper alloy precursor; in the process, the washing detergent is selected from deionized water and ethanol, and the washing times are 2-4 times; more specifically, the washing is performed 3 times by water and 3 times by ethanol; the drying temperature is 40-80 ℃, more specifically 60 ℃, and the drying time is 12 hours. The nickel salt is preferably a soluble inorganic nickel salt, more preferably nickel nitrate hexahydrate; the tungsten salt is preferably ammonium tungstate and ammonium metatungstate, more preferably ammonium metatungstate. The water is preferably deionized water. The atomic ratio of nickel salt to tungsten salt is preferably Ni: w is (2-5): 1, finally preferably Ni: w is 4: 1. the hydrothermal temperature is preferably 100-180 ℃, more preferably 120-150 ℃ and finally preferably 130 ℃. The hydrothermal time is preferably 6-12 h, and is more preferably 8 h. Also, the hydrothermal reaction is followed by washing, preferably 3 times in deionized water, and vacuum drying at 60 ℃ for 12 hours. In the process, a series of nanoflower structures taking nickel and tungsten as precursors are formed on the basis of forming the copper hydroxide nanowire array and are attached to the nanowires.
Carrying out heat treatment on the obtained initial composite nickel-tungsten-copper alloy precursor to obtain a composite nickel-tungsten-copper alloy; in the process, the composite nickel-tungsten-copper alloy consisting of the foam copper substrate and the nickel-tungsten-copper alloy nano particles which are loaded on the foam copper substrate and distributed in the shape of hollow nano tubes is obtained. The heat treatment is carried out under N2And 5% of H2The reaction is carried out in an Ar atmosphere at the temperature of 300-600 ℃ for 0.5-2 h; preferably, the atmosphere of the heat treatment is 5% H2Ar at 500 deg.c for 1 hr.
The invention further realizes the adjustment of the morphology of the alloy particles by a simple method for adjusting the proportion of reactants and the annealing temperature and time, and the obtained nickel-tungsten-copper alloy with hollow nano-tube-shaped distribution can be directly used as an alkaline hydrogen oxidation reaction catalyst and shows extremely high catalytic activity.
The composite nickel-tungsten-copper alloy prepared by the method consists of a foam copper substrate and a nickel-tungsten-copper alloy which is loaded on the foam copper substrate and is distributed in a hollow nano tube shape; the copper in the nickel-tungsten-copper alloy is obtained by carrying out hydrothermal reaction and heat treatment on a copper hydroxide nanowire array subjected to anodic oxidation of original foam copper.
The invention also provides the application of the composite nickel-tungsten-copper alloy in electrocatalysis alkaline hydrogen oxidation; specifically, the nickel-tungsten-copper alloy/copper foam is directly used as a catalyst for the hydrogen oxidation reaction; the electrolyte for the hydrogen oxidation reaction in the present invention is preferably a potassium hydroxide solution, and the concentration thereof is preferably 0.1 mol/L.
For further understanding of the present invention, the following examples are provided to illustrate the composite nickel-tungsten-copper alloy and the preparation method thereof, and the scope of the present invention is not limited by the following examples.
The reagents used in the following examples are all commercially available; the reactions of the examples and comparative examples were carried out under the same external conditions.
Example 1
Firstly, the foamy copper is ultrasonically cleaned in dilute hydrochloric acid, ethanol and deionized water for several times, then the foamy copper is cut into pieces of 1 × 4cm, and the pieces of the foamy copper are placed in 1mol/L sodium hydroxide solution of 15mA/cm2Performing anodic oxidation for 20min under constant current, taking a platinum sheet as a counter electrode, washing the obtained product with deionized water, and drying at 60 ℃ for 6h to obtain a copper hydroxide nanowire array/foamy copper;
putting the copper hydroxide nanowire array/foam copper obtained by anodic oxidation into a reactor with the atomic ratio of nickel salt to tungsten salt being 4: 1, performing hydrothermal reaction for 8 hours at 130 ℃, then washing and drying the solution, and performing reaction on the solution in 5% H2And reducing for 1h at 500 ℃ in an Ar atmosphere to obtain the product composite nickel-tungsten-copper alloy.
The composite nickel-tungsten-copper alloy obtained in example 1 was analyzed by a scanning electron microscope to obtain a scanning electron micrograph, which is shown in fig. 1.
The composite nickel-tungsten-copper alloy obtained in example 1 was analyzed by X-ray diffraction, and the X-ray crystal diffraction pattern thereof was obtained as shown in fig. 2.
Cutting the product into 1 × 1cm, directly using the product as a catalyst for a hydrogen oxidation reaction, using a carbon rod as a counter electrode, using a saturated calomel electrode as a reference electrode, using 0.1mol/L potassium hydroxide solution as electrolyte, and performing voltammetry scanning at a sweep rate of 1mV/s in a voltage range of 0-0.3V to obtain a polarization curve relative to a reversible hydrogen electrode, as shown in figures 3, 4 and 5, wherein the optimal platform current is up to 19.5mA/cm2。
Example 2
Copper hydroxide nanowire arrays/copper foams were prepared as described in example 1;
putting the copper hydroxide nanowire array/foam copper obtained by anodic oxidation into a reactor with the atomic ratio of nickel salt to tungsten salt being 2: 1, performing hydrothermal reaction for 8 hours at 130 ℃, then washing and drying the solution, and performing reaction on the solution in 5% H2And reducing for 1h at 500 ℃ in an Ar atmosphere to obtain the product composite nickel-tungsten-copper alloy.
The composite nickel-tungsten-copper alloy obtained in example 2 was analyzed by a scanning electron microscope to obtain a scanning electron micrograph, which is shown in fig. 6.
The composite nickel-tungsten-copper alloy obtained in example 2 was analyzed by X-ray diffraction, and the X-ray crystal diffraction pattern thereof was obtained as shown in fig. 2.
Example 3
Copper hydroxide nanowire arrays/copper foams were prepared as described in example 1;
putting the copper hydroxide nanowire array/foam copper obtained by anodic oxidation into a reactor with the atomic ratio of nickel salt to tungsten salt being 3: 1, performing hydrothermal reaction for 8 hours at 130 ℃, then washing and drying the solution, and performing reaction on the solution in 5% H2And reducing for 1h at 500 ℃ in an Ar atmosphere to obtain the product composite nickel-tungsten-copper alloy.
The composite nickel-tungsten-copper alloy obtained in example 3 was analyzed by a scanning electron microscope to obtain a scanning electron micrograph, which is shown in fig. 7.
The composite nickel-tungsten-copper alloy obtained in example 3 was analyzed by X-ray diffraction, and the X-ray crystal diffraction pattern thereof was obtained as shown in fig. 2.
Example 4
Copper hydroxide nanowire arrays/copper foams were prepared as described in example 1; the scanning electron microscope photo of the copper foam is shown in FIG. 8, and the scanning electron microscope photo of the copper hydroxide nanowire array/copper foam is shown in FIG. 9;
putting the copper hydroxide nanowire array/foam copper obtained by anodic oxidation into a reactor with the atomic ratio of nickel salt to tungsten salt being 5: 1, performing hydrothermal reaction for 8 hours at 130 ℃, then washing and drying the solution, and performing reaction on the solution in 5% H2Reducing for 1h at 500 ℃ in an Ar atmosphere to obtain the product. A scanning electron micrograph of the product obtained after the hydrothermal reaction is shown in fig. 10;
the composite nickel-tungsten-copper alloy obtained in example 4 was analyzed by a scanning electron microscope to obtain a scanning electron micrograph, which is shown in fig. 11 and fig. 12.
The composite nickel-tungsten-copper alloy obtained in example 4 was analyzed by X-ray diffraction, and the X-ray crystal diffraction pattern thereof was obtained as shown in fig. 2.
Example 5
Copper hydroxide nanowire arrays/copper foams were prepared as described in example 1;
putting the copper hydroxide nanowire array/foam copper obtained by anodic oxidation into a reactor with the atomic ratio of nickel salt to tungsten salt being 4: 1, performing hydrothermal reaction for 8 hours at 130 ℃, then washing and drying the solution, and performing reaction on the solution in 5% H2And reducing for 1h at 300 ℃ under Ar atmosphere to obtain the product.
The composite nickel-tungsten-copper alloy obtained in example 5 was analyzed by a scanning electron microscope to obtain a scanning electron micrograph, which is shown in fig. 13.
Example 6
Copper hydroxide nanowire arrays/copper foams were prepared as described in example 1;
putting the copper hydroxide nanowire array/foam copper obtained by anodic oxidation into a reactor with the atomic ratio of nickel salt to tungsten salt being 4: 1, performing hydrothermal reaction for 8 hours at 130 ℃, then washing and drying the solution, and performing reaction on the solution in 5% H2Reducing for 1h at 400 ℃ under Ar atmosphere to obtain the product.
The composite nickel-tungsten-copper alloy obtained in example 6 was analyzed by a scanning electron microscope to obtain a scanning electron micrograph, which is shown in fig. 14.
Example 7
Copper hydroxide nanowire arrays/copper foams were prepared as described in example 1;
putting the copper hydroxide nanowire array/foam copper obtained by anodic oxidation into a reactor with the atomic ratio of nickel salt to tungsten salt being 4: 1, performing hydrothermal reaction for 8 hours at 130 ℃, then washing and drying the solution, and performing reaction on the solution in 5% H2Reducing for 1h at 600 ℃ under Ar atmosphere to obtain the product.
The composite nickel-tungsten-copper alloy obtained in example 7 was analyzed by a scanning electron microscope to obtain a scanning electron micrograph, which is shown in fig. 15.
Example 8
Copper hydroxide nanowire arrays/copper foams were prepared as described in example 1;
oxidizing the anode to obtain hydrogen hydroxidePutting the copper nanowire array/foam copper into a reactor with the atomic ratio of nickel salt to tungsten salt being 4: 1, performing hydrothermal reaction for 8 hours at 130 ℃, then washing and drying the solution, and performing reaction on the solution in 5% H2Reducing for 0.5h at 500 ℃ in Ar atmosphere to obtain the product.
The composite nickel-tungsten-copper alloy obtained in example 8 was analyzed by a scanning electron microscope to obtain a scanning electron micrograph, which is shown in fig. 16.
Example 9
Copper hydroxide nanowire arrays/copper foams were prepared as described in example 1;
putting the copper hydroxide nanowire array/foam copper obtained by anodic oxidation into a reactor with the atomic ratio of nickel salt to tungsten salt being 4: 1, performing hydrothermal reaction for 8 hours at 130 ℃, then washing and drying the solution, and performing reaction on the solution in 5% H2Reducing for 1.5h at 500 ℃ in Ar atmosphere to obtain the product.
The composite nickel-tungsten-copper alloy obtained in example 9 was analyzed by a scanning electron microscope to obtain a scanning electron micrograph, which is shown in fig. 17.
Example 10
Copper hydroxide nanowire arrays/copper foams were prepared as described in example 1;
putting the copper hydroxide nanowire array/foam copper obtained by anodic oxidation into a reactor with the atomic ratio of nickel salt to tungsten salt being 4: 1, performing hydrothermal reaction for 8 hours at 130 ℃, then washing and drying the solution, and performing reaction on the solution in 5% H2Reducing for 2.0h at 500 ℃ in Ar atmosphere to obtain the product.
The composite nickel-tungsten-copper alloy obtained in example 10 was analyzed by a scanning electron microscope to obtain a scanning electron micrograph, which is shown in fig. 18.
Comparative example 1
Copper hydroxide nanowire arrays/copper foams were prepared as described in example 1;
putting the copper hydroxide nanowire array/foam copper obtained by anodic oxidation into a precursor solution only containing 2mmol of nickel salt, carrying out hydrothermal reaction for 8H at 130 ℃, then washing and drying, and carrying out reaction under 5% H2Reducing for 1h at 500 ℃ in an Ar atmosphere to obtain the product.
The composite nickel-copper alloy obtained in comparative example 1 was analyzed by a scanning electron microscope to obtain a scanning electron micrograph, which is shown in fig. 19.
The product is cut into 1 × 1cm, and directly used as a catalyst for the hydrogen oxidation reaction, a carbon rod is used as a counter electrode, a saturated calomel electrode is used as a reference electrode, 0.1mol/L potassium hydroxide solution is used as electrolyte, voltammetry scanning is carried out at a scanning speed of 1mV/s in a voltage range of 0-0.3V, and a polarization curve relative to a reversible hydrogen electrode is obtained, as shown in FIG. 3.
The above description of the embodiments is only intended to facilitate the understanding of the method of the invention and its core idea. It should be noted that, for those skilled in the art, it is possible to make various improvements and modifications to the present invention without departing from the principle of the present invention, and those improvements and modifications also fall within the scope of the claims of the present invention.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (9)
1. A preparation method of a composite nickel-tungsten-copper alloy comprises the following steps:
A) cleaning the foamy copper and then carrying out anodic oxidation in a sodium hydroxide solution to obtain a copper hydroxide nanowire array/foamy copper compound;
B) carrying out hydrothermal reaction on the copper hydroxide nanowire array/foam copper compound, nickel salt, tungsten salt and water, and carrying out vacuum drying to obtain an initial composite nickel-tungsten-copper alloy precursor;
C) and carrying out heat treatment on the initial composite nickel-tungsten-copper alloy precursor to obtain the composite nickel-tungsten-copper alloy.
2. The method according to claim 1, wherein the concentration of the sodium hydroxide solution is 1 to 2 mol/L.
3. The preparation method according to claim 1, wherein the anodic oxidation current density is constant current of 10-20 mA/cm2The time is 10-30 min.
4. The production method according to claim 1, wherein the atomic ratio of nickel to tungsten in the nickel salt and the tungsten salt is (2 to 5): 1.
5. the preparation method according to claim 1, wherein the hydrothermal reaction is carried out at a temperature of 120-150 ℃ for 6-12 hours.
6. The method of claim 1, wherein the heat treatment is at 5% H2The reaction is carried out in an Ar atmosphere at the temperature of 300-600 ℃ for 0.5-2 h.
7. The method according to claim 1, wherein the washing is ultrasonic washing in dilute hydrochloric acid, ethanol and deionized water in this order.
8. The composite nickel-tungsten-copper alloy prepared by the preparation method of any one of claims 1 to 7 consists of a foamed copper substrate and a nickel-tungsten-copper alloy which is loaded on the foamed copper substrate and is distributed in a hollow nano tube shape.
9. The use of the composite nickel-tungsten-copper alloy prepared by the preparation method of any one of claims 1 to 7 or the composite nickel-tungsten-copper alloy of claim 8 in electrocatalytic alkaline hydrogen oxidation.
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