CN113215617B - Copper nanowire loaded CoNi nanosheet electrocatalyst and preparation method and application thereof - Google Patents

Copper nanowire loaded CoNi nanosheet electrocatalyst and preparation method and application thereof Download PDF

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CN113215617B
CN113215617B CN202110504427.5A CN202110504427A CN113215617B CN 113215617 B CN113215617 B CN 113215617B CN 202110504427 A CN202110504427 A CN 202110504427A CN 113215617 B CN113215617 B CN 113215617B
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郑瑞娟
钟坚海
张艳燕
叶华欣
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Longyan Entry And Exit Comprehensive Detection Technology Services Center
Longyan University
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Abstract

The invention provides a copper nanowire supported CoNi nanosheet electrocatalyst and a preparation method and application thereof, and belongs to the technical field of electrocatalysis. Copper foam is used as a base material, copper hydroxide nanowires are generated through chemical oxidation reaction, electrochemical reduction is carried out to generate copper nanowires, and then CoNi nanosheets are loaded on the copper nanowires through electrochemical deposition, so that the copper nanowire loaded CoNi nanosheets electrocatalyst is obtained. The porous foam copper is used as a substrate material, and the copper nanowires are generated on the surface of the porous foam copper in situ and then loaded with CoNi nano sheets, so that the surface area of the substrate is increased, good conductivity is kept, and meanwhile, compared with a noble metal catalyst, the Co and Ni transition metal catalyst is low in price, easy to prepare and excellent in performance.

Description

Copper nanowire loaded CoNi nanosheet electrocatalyst and preparation method and application thereof
Technical Field
The invention relates to the technical field of electrocatalysis, in particular to a copper nanowire supported CoNi nanosheet electrocatalyst, a preparation method and application thereof.
Background
With the increasing energy crisis and environmental pollution, development of new clean energy has been urgent. Hydrogen is a clean energy source and has great application potential. The hydrogen production by water electrolysis is a novel hydrogen production technology, and has the advantages of high efficiency, environmental friendliness, high safety and the like, and has wide application prospect. At present, the key of the technology for producing hydrogen by electrolyzing water is to find a novel efficient catalyst. However, in practical applications, existing catalytic materials still face the following problems: on one hand, the existing catalytic material is generally prepared into catalyst powder firstly, then the catalyst powder is fixed on the surface of an electrode through a binder, a sample is easy to fall off, and the use of the binder influences the full contact between the catalyst and electrolyte, so that the internal resistance is increased, and the catalytic activity and the stability of the electrode are influenced; on the other hand, noble metal Pt is currently an electrolytic water hydrogen production catalyst with higher activity, but its large-scale application in industrial and commercial production is limited due to its high price, low reserves and the like. Thus, it is very important to prepare inexpensive, high activity, stable non-noble metal catalysts.
Disclosure of Invention
In order to solve the technical problems, the invention provides a copper nanowire supported CoNi nanosheet electrocatalyst, and a preparation method and application thereof; the foamed copper with a porous structure is selected as a substrate material, and after copper nanowires are generated on the surface of the foamed copper in situ, coNi nano sheets are loaded, so that the surface area of the substrate is increased, good conductivity is kept, and meanwhile, compared with a noble metal catalyst, co and Ni transition metals are low in price, easy to prepare and excellent in performance.
According to one of the technical schemes of the invention, a copper nanowire loaded CoNi nano-sheet electrocatalyst is provided, and CoNi nano-sheets are loaded on copper nanowires generated on the surface of a foam copper base material in situ.
Further, the copper nanowire is of a bent structure, and the molar concentration ratio of Co to Ni is 1:1,1:2 or 2:1.
According to the preparation method of the copper nanowire supported CoNi nanosheet electrocatalyst, foam copper is used as a base material, copper hydroxide nanowires are generated through chemical oxidation reaction, electrochemical reduction is carried out to generate copper nanowires with bent structures, and then the copper nanowire supported CoNi nanosheet electrocatalyst is obtained through electrochemical deposition. The copper nanowire with the bending structure enhances the conductivity of the electrode and is more beneficial to the loading of the subsequent CoNi active substances.
Further, copper foam is used as a base material by reacting NaOH and (NH 4 ) 2 S 2 O 8 Chemical oxidation in mixed solution a of (2) to generate copper hydroxide nanowire, then in Na 2 SO 4 Electrochemical reduction in solution to generate copper nano wire, and finally in CoCl 2 And NiCl 2 And (3) carrying out electrochemical deposition in the mixed solution b by adopting a cyclic voltammetry, and then cleaning and drying to obtain the copper nanowire supported CoNi nanosheet electrocatalyst.
Further, the concentration of NaOH in the mixed solution a is 2mol/L, (NH) 4 ) 2 S 2 O 8 The concentration of (2) is 0.2mol/L; the Na is 2 SO 4 The concentration of the solution is 1mol/L; coCl in the mixed solution b 2 And NiCl 2 The mass concentration ratio of the substances is 1:2, 2:1 or 1:1, and the CoCl is that 2 And NiCl 2 The total concentration in the mixed solution b is 0.2-0.3mol/L.
Further, the electrochemical reduction current density is-20 mA/cm 2 The electrochemical reduction time is 15min; the electrochemical deposition conditions of the cyclic voltammetry are as follows: scanning range from 0.2 to-1.2V, scanning speed of 25mV/s, and scanning for 5-50 circles.
Further, the drying is vacuum drying at 60 ℃ for 4 hours.
In the technical scheme of the invention, the copper foam material with a three-dimensional structure is selected as a base material, so that the surface area is larger than that of the existing plate electrode, the loading of active substances is facilitated, and meanwhile, the concentration of the reaction solution in the mixed solution a in the chemical oxidation process is limited, so that Cu (OH) with uniform size is generated on the surface of the copper foam in situ 2 Nanowires, increase the surface area of the base material. In the process of reducing copper hydroxide nano wire, na is selected 2 SO 4 Electrochemical reduction in solution, on the one hand, makes the reduction process controllable, and helps to reduce Cu (OH) compared with chemical reduction method 2 The nanowires are all converted into copper nanowires, and on the other hand, the reduced copper nanowire structures are bent and interwoven together, so that the conductivity and the stability of the substrate material are improved. In the electrochemical deposition process by adopting the cyclic voltammetry, cobalt and nickel ions are limited, and electrochemical deposition parameters are defined, so that cobalt and nickel catalysts loaded on the surface of the copper nanowire are in nano-scale, and Co and Ni are used forThe catalytic performance of the Ni catalyst is better than that of Co alone.
The third technical scheme of the invention is the application of the copper nanowire-supported CoNi nanosheet electrocatalyst in hydrogen production by water electrolysis.
Compared with the prior art, the invention has the beneficial effects that:
the three-dimensional skeleton structure is constructed for the catalyst by adopting the foamy copper as a base material, so that the material structure is optimized, the product has larger specific surface area, the loading amount of active substances is increased, more reactive sites are provided for the reaction, the electrolyte is fully contacted with the electrode material, the internal resistance of the electrode is greatly reduced, the transmission of ions and electrons is increased, the electrochemical activity is greatly improved, the material transmission is facilitated, and the generated gas overflows in time.
Aiming at the technical problem that the traditional powder transition metal catalyst needs an adhesive, the invention provides the Cu nanowire electrode with large surface area and good conductivity as a substrate electrode, and the CoNi nano-sheet electrocatalyst is electrochemically deposited on the substrate electrode in situ. The method can not only effectively avoid various problems caused by using the adhesive and improve the conductivity and the stability, but also is simple and quick, low in cost and wide in application prospect. Meanwhile, as the invention is the electrocatalyst directly growing on the three-dimensional foam copper substrate, a three-dimensional framework structure is constructed for the catalyst, the material structure is optimized, the product has larger specific surface area, the loading amount of active substances is increased, each nano structure participates in the electrochemical reaction to provide more reactive sites for the reaction, the electrolyte is fully contacted with the electrode material, the internal resistance of the electrode is greatly reduced, the transmission of ions and electrons is increased, the electrochemical activity is greatly improved, the material transmission is facilitated, and the generated gas overflows in time.
The copper nanowire loaded CoNi nanosheet electrocatalyst prepared by the method is nontoxic, simple to operate, high in selectivity, low in cost and wide in application prospect.
Drawings
FIG. 1 is a schematic diagram of the preparation of a copper nanowire supported CoNi nanoplatelet electrocatalyst according to example 1 of the invention;
FIG. 2 is an X-ray photoelectron spectroscopy (XPS) chart of a copper nanowire supported CoNi nanosheet electrocatalyst prepared in example 1 of the invention; wherein A is a full spectrum scanning result, B is a Cu2p scanning result, C is a Ni 2p section scanning result, and D is a Co 2p scanning result;
FIG. 3 is an energy scattering x-ray spectroscopy (EDS) spectrum of a copper nanowire supported CoNi nanoplatelet electrocatalyst prepared according to example 1 of the invention;
FIG. 4 is a scanning electron microscope image of the raw materials and the products in the process of preparing the copper nanowire supported CoNi nanosheet electrocatalyst according to example 1 of the invention; wherein A is commercial foamy copper, B is Cu (OH) obtained by chemical oxidation 2 The nanowire C is a Cu nanowire obtained by electrochemical reduction, and D is a copper nanowire loaded CoNi nanosheet;
FIG. 5 is a transmission electron microscope image of a copper nanowire supported CoNi nanosheet electrocatalyst prepared in example 1 of the invention;
FIG. 6 is a graph showing electrocatalytic hydrogen production performance of copper nanowire supported CoNi nanoplatelets electrocatalyst, raw materials and intermediates prepared in example 1 of the invention;
FIG. 7 is a Cu nanowire and Cu (OH) prepared in example 1 2 XRD pattern of nanowires;
FIG. 8 is a graph showing the comparison of electrochemical hydrogen production performance of copper nanowire-supported CoNi nanoplates prepared with different number of scanning turns;
FIG. 9 is a graph showing the comparison of electrochemical hydrogen production performance of copper nanowire-supported CoNi nanoplates prepared from different proportions of Co and Ni;
FIG. 10 is a graph comparing electrochemical hydrogen production performance of copper nanowire-loaded Co nanoplates alone and copper nanowire-loaded CoNi nanoplates;
FIG. 11 is a graph comparing electrochemical hydrogen production performance of copper nanowire-loaded Ni nanoplates alone and copper nanowire-loaded CoNi nanoplates.
Detailed Description
Various exemplary embodiments of the invention will now be described in detail, which should not be considered as limiting the invention, but rather as more detailed descriptions of certain aspects, features and embodiments of the invention.
It is to be understood that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. In addition, for numerical ranges in this disclosure, it is understood that each intermediate value between the upper and lower limits of the ranges is also specifically disclosed. Every smaller range between any stated value or stated range, and any other stated value or intermediate value within the stated range, is also encompassed within the invention. The upper and lower limits of these smaller ranges may independently be included or excluded in the range.
Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. Although only preferred methods and materials are described herein, any methods and materials similar or equivalent to those described herein can be used in the practice or testing of the present invention. All documents mentioned in this specification are incorporated by reference for the purpose of disclosing and describing the methods and/or materials associated with the documents. In case of conflict with any incorporated document, the present specification will control.
It will be apparent to those skilled in the art that various modifications and variations can be made in the specific embodiments of the invention described herein without departing from the scope or spirit of the invention. Other embodiments will be apparent to those skilled in the art from consideration of the specification of the present invention. The specification and examples are exemplary only.
As used herein, the terms "comprising," "including," "having," "containing," and the like are intended to be inclusive and mean an inclusion, but not limited to.
Example 1
The copper foam was placed in 2mol/L NaOH and 0.2mol/L (NH) 4 ) 2 S 2 O 8 Soaking in the mixture solution for 20min, taking out, and washing to obtain Cu (OH) 2 A nanowire. Then put in 1mol/L Na 2 SO 4 The current density adopted in the solution is-20 mA/cm 2 Constant current reduction for 15min, taking out, washing, and drying in vacuum drying oven to obtain Cu nanometerA wire. Then the Cu nanowire electrode was placed at 30mL of CoCl with a concentration of 0.1mol/L 2 And 0.1mol/L NiCl 2 And (3) in the mixed solution, adopting a cyclic voltammetry, scanning at a scanning speed of 25mV/s and a scanning range of 0.2 to-1.2V, scanning for 25 circles, taking out, washing, and drying in a vacuum drying oven at 60 ℃ for 4 hours to obtain the copper nanowire-supported CoNi nanosheet electrocatalyst.
The schematic diagram of the preparation of the copper nanowire-supported CoNi nanosheet electrocatalyst in the embodiment is shown in fig. 1; analysis of the prepared material is carried out, the X-ray photoelectron spectrum (XPS) of the CoNi nano-sheet electrocatalyst loaded by the copper nano-wire is shown in figure 2, the existence of Cu, co and Ni elements in a sample can be judged according to the position of the characteristic spectrum of figure 2A, the XPS spectrum of figure 2B Cu2p is found after the spectrum is fitted, two obvious sustaining peaks which are positioned at 932.54eV and 952.33eV can be fitted in the spectrum, and the two characteristic peaks are Cu2p respectively 3/2 And Cu2p 1/2 Binding energy of (a); FIGS. 2C,778.81 and 794.44eV are Co 2+ 2p 3/2 And Co 2+ 2p 1/2 Characteristic peaks of binding energy of (2); FIGS. 2D,853.45eV and 870.65eV are Ni 2+ 2p 3/2 And Ni 2+ 2p 1/2 Characteristic peak of binding energy. The EDS spectrum of the copper nanowire loaded CoNi nanosheet electrocatalyst is shown in fig. 3, and the electrode surface is successfully loaded with CoNi according to fig. 3; scanning electron microscope images of raw materials and products in the process of preparing the copper nanowire supported CoNi nanosheet electrocatalyst are shown in figure 4; wherein FIG. 4A is a commercial copper foam and FIG. 4B is Cu (OH) obtained by chemical oxidation 2 Nanowires, fig. 4C is a Cu nanowire obtained by electrochemical reduction, and fig. 4D is a copper nanowire-supported CoNi nanosheet; from FIG. 4, it can be seen that the surface of commercially available copper foam is smooth, and Cu (OH) is uniformly formed on the surface of copper foam after chemical oxidation 2 Nanowires, in Na 2 SO 4 Electrochemical reduction in the solution is carried out to generate bent crisscrossed Cu nanowires, and CoNi nano sheets are uniformly loaded on the surfaces of the Cu nanowires through electrochemical deposition; the transmission electron microscope image of the prepared copper nanowire supported CoNi nano-sheet electrocatalyst is shown in fig. 5, and the result of fig. 5 is that the CoNi nano-sheet is uniformly supported on the surface of the copper nanowire.
The electrochemical hydrogen production performance verification is carried out on the prepared copper nanowire loaded CoNi nanosheet electrocatalyst, and the specific process is as follows:
the method comprises the steps of adopting a three-electrode system, adopting a copper nanowire loaded CoNi nano-sheet electrode as a working electrode, adopting a carbon rod electrode as a counter electrode and adopting a reference electrode of a saturated calomel electrode, and adopting a linear scanning voltammetry in a KOH solution of 1mol/L, wherein the scanning rate is 2mV/s.
The hydrogen production performance results of the product, the raw material and the intermediate product prepared in this example are shown in fig. 6, wherein fig. 6a is an electrocatalytic hydrogen production curve of untreated foam copper, fig. 6b is an electrocatalytic hydrogen production curve of copper nanowires, and fig. 6c is an electrocatalytic hydrogen production curve of copper nanowire-supported CoNi nanosheets. Commercial copper foam has poor electrocatalytic performance, and when the overpotential is 450mV, the current density is still insufficient to be 10mA/cm 2 . The electrochemical hydrogen production performance of the reduced copper nanowire electrode is obviously enhanced, and when the current density is 10mA/cm 2 The overpotential was 365mV. When the CoNi nano-sheet is modified on the copper nano-wire electrode, the electrochemical hydrogen production performance of the electrode is best, when the current density is 10mA/cm 2 The overpotential was only 49mV. FIG. 7 shows Cu nanowires and Cu (OH) prepared in example 1 2 XRD patterns (a) and Cu (OH) of nanowires 2 Nanowire (b), cu (OH) is available from FIG. 7 2 The nanowires are completely converted into copper nanowires.
Example 2
The copper foam was placed in 2mol/L NaOH and 0.2mol/L (NH) 4 ) 2 S 2 O 8 Soaking in the mixture solution for 20min, taking out, and washing to obtain Cu (OH) 2 A nanowire. Then put in 1mol/L Na 2 SO 4 The current density adopted in the solution is-20 mA/cm 2 And (5) constant-current reduction is carried out for 15min, the Cu nanowire is taken out and washed clean, and is placed in a vacuum drying oven for drying, so that the Cu nanowire is obtained. Then the Cu nanowire electrode was placed at 30mL of CoCl with a concentration of 0.1mol/L 2 And 0.1mol/L NiCl 2 And (3) in the mixed solution, adopting a cyclic voltammetry, scanning at a scanning speed of 25mV/s and a scanning range of 0.2 to-1.2V for 5 circles, taking out, washing, and drying in a vacuum drying oven at 60 ℃ for 4 hours to obtain the copper nanowire-supported CoNi nanosheet electrocatalyst.
Example 3
The copper foam was placed in 2mol/L NaOH and 0.2mol/L (NH) 4 ) 2 S 2 O 8 Soaking in the mixture solution for 20min, taking out, and washing to obtain Cu (OH) 2 A nanowire. Then put in 1mol/L Na 2 SO 4 The current density adopted in the solution is-20 mA/cm 2 And (5) constant-current reduction is carried out for 15min, the Cu nanowire is taken out and washed clean, and is placed in a vacuum drying oven for drying, so that the Cu nanowire is obtained. Then the Cu nanowire electrode was placed at 30mL of CoCl with a concentration of 0.1mol/L 2 And 0.1mol/L NiCl 2 And (3) in the mixed solution, adopting a cyclic voltammetry, scanning at a scanning speed of 25mV/s and a scanning range of 0.2 to-1.2V for 50 circles, taking out, washing, and drying in a vacuum drying oven at 60 ℃ for 4 hours to obtain the copper nanowire-supported CoNi nanosheet electrocatalyst.
The difference between the example 1 and the examples 2 and 3 is that the number of scanning turns is different, and the same experimental method as that of the example 1 is adopted to verify the performance of the products of the examples 2 to 3, and the results are shown in fig. 8; when the number of scanning turns is 5, the crystallization performance is not good, and the electrochemical hydrogen production is poor. The hydrogen production performance is best when the deposition turns are 25 turns. When the number of scanning turns is 50, the deposited CoNi nano sheets are too thick, so that the deposited CoNi nano sheets are accumulated on the surface of the electrode, the surface area is reduced, the conductivity is poor, and the electrochemical hydrogen production performance is poor.
Example 4
The copper foam was placed in 2mol/L NaOH and 0.2mol/L (NH) 4 ) 2 S 2 O 8 Soaking in the mixture solution for 20min, taking out, and washing to obtain Cu (OH) 2 A nanowire. Then put in 1mol/L Na 2 SO 4 The current density adopted in the solution is-20 mA/cm 2 And (5) constant-current reduction is carried out for 15min, the Cu nanowire is taken out and washed clean, and is placed in a vacuum drying oven for drying, so that the Cu nanowire is obtained. Then the Cu nanowire electrode was placed at 30mL of CoCl with a concentration of 0.2mol/L 2 And 0.1mol/L NiCl 2 And (3) in the mixed solution, adopting a cyclic voltammetry, scanning at a scanning speed of 25mV/s and a scanning range of 0.2 to-1.2V, scanning for 25 circles, taking out, washing, and drying in a vacuum drying oven at 60 ℃ for 4 hours to obtain the copper nanowire-supported CoNi nanosheet electrocatalyst.
Example 5
Foam is madeCopper is placed in 2mol/L NaOH and 0.2mol/L (NH) 4 ) 2 S 2 O 8 Soaking in the mixture solution for 20min, taking out, and washing to obtain Cu (OH) 2 A nanowire. Then put in 1mol/L Na 2 SO 4 The current density adopted in the solution is-20 mA/cm 2 And (5) constant-current reduction is carried out for 15min, the Cu nanowire is taken out and washed clean, and is placed in a vacuum drying oven for drying, so that the Cu nanowire is obtained. Then the Cu nanowire electrode was placed at 30mL of CoCl with a concentration of 0.1mol/L 2 And 0.2mol/L NiCl 2 And (3) in the mixed solution, adopting a cyclic voltammetry, scanning at a scanning speed of 25mV/s and a scanning range of 0.2 to-1.2V, scanning for 25 circles, taking out, washing, and drying in a vacuum drying oven at 60 ℃ for 4 hours to obtain the copper nanowire-supported CoNi nanosheet electrocatalyst.
Example 4, example 5 and example 1 differ in the concentration of cobalt and nickel ions, and the same experimental method as in example 1 was used to verify the performance of the products of examples 4-5, and the results show that the electrocatalytic hydrogen production performance is best when the ratio of cobalt and nickel ion concentrations is 1:1 as shown in fig. 9.
Example 6
The copper foam was placed in 2mol/L NaOH and 0.2mol/L (NH) 4 ) 2 S 2 O 8 Soaking in the mixture solution for 20min, taking out, and washing to obtain Cu (OH) 2 A nanowire. Then put in 1mol/L Na 2 SO 4 The current density adopted in the solution is-20 mA/cm 2 And (5) constant-current reduction is carried out for 15min, the Cu nanowire is taken out and washed clean, and is placed in a vacuum drying oven for drying, so that the Cu nanowire is obtained. Then the Cu nanowire electrode was placed at 30mL of CoCl with a concentration of 0.2mol/L 2 And (3) in the solution, adopting a cyclic voltammetry, scanning at a scanning speed of 25mV/s and a scanning range of 0.2 to-1.2V, scanning for 25 circles, taking out, washing cleanly, and drying in a vacuum drying oven at 60 ℃ for 4 hours to obtain the copper nanowire-supported Co nanosheet electrocatalyst.
The electrochemical hydrogen production performance of the prepared catalyst and the product of the example 1 are compared, and the result is shown in fig. 10, wherein a curve a is the electrochemical hydrogen production performance of the copper nanowire-supported Co nano-plate alone, and a curve b is the electrochemical hydrogen production performance of the copper nanowire-supported CoNi nano-plate. As can be seen from fig. 10, the electrochemical hydrogen production performance of the product obtained by independently loading Co is not as good as that of the copper nanowire loaded CoNi nanosheets.
Example 7
The copper foam was placed in 2mol/L NaOH and 0.2mol/L (NH) 4 ) 2 S 2 O 8 Soaking in the mixture solution for 20min, taking out, and washing to obtain Cu (OH) 2 A nanowire. Then put in 1mol/L Na 2 SO 4 The current density adopted in the solution is-20 mA/cm 2 And (5) constant-current reduction is carried out for 15min, the Cu nanowire is taken out and washed clean, and is placed in a vacuum drying oven for drying, so that the Cu nanowire is obtained. Then the Cu nanowire electrode was placed in 30mL of NiCl with a concentration of 0.2mol/L 2 And (3) in the solution, adopting a cyclic voltammetry, scanning at a scanning speed of 25mV/s and a scanning range of 0.2 to-1.2V, scanning for 25 circles, taking out, washing cleanly, and drying in a vacuum drying oven at 60 ℃ for 4 hours to obtain the copper nanowire-loaded Ni nanosheet electrocatalyst.
The electrochemical hydrogen production performance of the prepared catalyst and the product of the example 1 are compared, and the result is shown in fig. 11, wherein a curve a is the electrochemical hydrogen production performance of the copper nanowire-supported Ni nano-sheet alone, and a curve b is the electrochemical hydrogen production performance of the copper nanowire-supported CoNi nano-sheet. As can be seen from fig. 11, the electrochemical hydrogen production performance of the product obtained by independently loading Ni is not as good as that of the copper nanowire loaded CoNi nanosheet.
The foregoing description of the preferred embodiments of the invention is not intended to limit the invention to the particular embodiments disclosed, but on the contrary, the intention is to cover all modifications, equivalents, and alternatives falling within the spirit and scope of the invention.

Claims (4)

1. A copper nanowire loaded CoNi nanosheet electrocatalyst is characterized in that: the CoNi nano-sheets are loaded on copper nano-wires generated on the surface of the foam copper substrate material in situ;
the copper nanowire is of a bending structure, and the molar concentration ratio of Co to Ni is 1:1,1:2 or 2:1;
the preparation method of the copper nanowire supported CoNi nanosheet electrocatalyst comprises the following steps: copper foam is used as a base material, and is prepared by mixing NaOH and (NH) 4 ) 2 S 2 O 8 Chemistry in mixed solution a of (2)Oxidizing to generate copper hydroxide nano-wire, then in Na 2 SO 4 Electrochemical reduction in solution to generate copper nano wire, and finally in CoCl 2 And NiCl 2 Carrying out electrochemical deposition in the mixed solution b by adopting a cyclic voltammetry, and then cleaning and drying to obtain the copper nanowire supported CoNi nanosheet electrocatalyst;
the concentration of NaOH in the mixed solution a is 2mol/L, (NH) 4 ) 2 S 2 O 8 The concentration of (2) is 0.2mol/L; the Na is 2 SO 4 The concentration of the solution is 1mol/L; coCl in the mixed solution b 2 And NiCl 2 The mass concentration ratio of the substances is 1:2, 2:1 or 1:1, and the CoCl is that 2 And NiCl 2 The total concentration in the mixed solution b is 0.2-0.3mol/L;
the electrochemical deposition conditions of the cyclic voltammetry are as follows: scanning range from 0.2 to-1.2V, scanning speed of 25mV/s, and scanning for 5-50 circles.
2. The copper nanowire-supported CoNi nanosheet electrocatalyst according to claim 1, wherein: the electrochemical reduction current density is-20 mA/cm 2 The electrochemical reduction time was 15min.
3. The copper nanowire-supported CoNi nanosheet electrocatalyst according to claim 1, wherein: the drying is vacuum drying at 60 ℃ for 4 hours.
4. Use of a copper nanowire-supported CoNi nanoplatelet electrocatalyst according to any one of claims 1 to 3 for hydrogen production by electrolysis of water.
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