CN115709083A - CuS @ NiCo LDH core-shell composite material and preparation method and application thereof - Google Patents
CuS @ NiCo LDH core-shell composite material and preparation method and application thereof Download PDFInfo
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- 238000006243 chemical reaction Methods 0.000 claims abstract description 10
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- QXZUUHYBWMWJHK-UHFFFAOYSA-N [Co].[Ni] Chemical compound [Co].[Ni] QXZUUHYBWMWJHK-UHFFFAOYSA-N 0.000 claims abstract description 8
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- 229910017052 cobalt Inorganic materials 0.000 claims description 3
- 239000010941 cobalt Substances 0.000 claims description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 3
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 2
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims description 2
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 2
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 2
- 229910000361 cobalt sulfate Inorganic materials 0.000 claims description 2
- 229940044175 cobalt sulfate Drugs 0.000 claims description 2
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 claims description 2
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 2
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 2
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 2
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims 1
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- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 14
- 239000008103 glucose Substances 0.000 description 14
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
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- 238000002484 cyclic voltammetry Methods 0.000 description 4
- JEGUKCSWCFPDGT-UHFFFAOYSA-N h2o hydrate Chemical compound O.O JEGUKCSWCFPDGT-UHFFFAOYSA-N 0.000 description 4
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- GFHNAMRJFCEERV-UHFFFAOYSA-L cobalt chloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].[Cl-].[Co+2] GFHNAMRJFCEERV-UHFFFAOYSA-L 0.000 description 3
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- QGUAJWGNOXCYJF-UHFFFAOYSA-N cobalt dinitrate hexahydrate Chemical compound O.O.O.O.O.O.[Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O QGUAJWGNOXCYJF-UHFFFAOYSA-N 0.000 description 1
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- AOPCKOPZYFFEDA-UHFFFAOYSA-N nickel(2+);dinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O AOPCKOPZYFFEDA-UHFFFAOYSA-N 0.000 description 1
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Abstract
The invention discloses a CuS @ NiCo LDH core-shell composite material and a preparation method and application thereof, wherein the method comprises the following steps: mixing Cu 2 Dispersing the O in an ethanol/deionized water mixed solution, and performing ultrasonic treatment to obtain a mixed solution A; then, sodium sulfide solution is dripped into the mixed solution A for reaction and centrifugation to obtain Cu 2 O @ CuS @ composite structure; dispersing the mixed solution and a nickel-cobalt source in an ethanol/deionized water mixed solution to obtain a mixed solution B, adding polyvinylpyrrolidone into the mixed solution B, and stirring to obtain a mixed solution C; and dripping a pentahydrate sodium thiosulfate solution into the mixed solution C for reaction, centrifuging, collecting the precipitate, washing and drying to obtain the CuS @ NiCo LDH core-shell composite material. Using cubic Cu 2 The method is characterized in that O is used as a template, a vulcanization and corrosion and deposition path is adopted, the nano hollow CuS @ NiCo LDH core-shell composite cube is prepared for the first time, and the obvious electrocatalytic activity is shown.
Description
Technical Field
The invention relates to the technical field of electrocatalytic materials, in particular to a CuS @ NiCo LDH core-shell composite material and a preparation method and application thereof.
Background
To control blood glucose levels in blood and effectively inhibit and diagnose diabetes, the development of highly sensitive, highly accurate electrochemical sensors for glucose is a hot spot of current research. At present, electrochemical sensors using enzymes as sensitive element materials have been commercialized due to their good selectivity, but still face fatal drawbacks. The inherent nature of enzymatic catalysts renders such sensors susceptible to environmental influences during use, thereby losing catalytic activity. Based on this, non-enzymatic electrochemical sensors that directly utilize the principle of electrooxidation are attracting much attention, and the design of non-enzymatic electrocatalysts offers the advantages of high sensitivity, low detection limit, fast response, simple operation, and the like. In the electrode material of the enzyme-free sensor, the transition metal catalyst has high application potential and value in glucose detection due to high electrooxidation activity, excellent electrochemical stability and low cost. Among them, layered Double Hydroxides (LDHs) based on transition metals have an ideal tunable electronic structure, and a new approach has been taken in recent years in the field of electrical analysis. However, two-dimensional nanostructured LDHs are prone to agglomeration in practical applications, leading to a reduction in active sites and slow electrocatalytic kinetics.
Therefore, in order to solve the above technical problems, it is necessary to develop a new electrocatalytic material.
Disclosure of Invention
The invention aims to provide a CuS @ NiCo LDH core-shell composite material, a preparation method and application thereof.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect of the invention, there is provided a method of preparing a cus@ nico LDH core-shell composite material, the method comprising:
mixing Cu 2 Dispersing the O in the ethanol/deionized water mixed solution, and performing ultrasonic treatment to obtain a mixed solution A; then, dropwise adding a sodium sulfide solution into the mixed solution A for reaction, and centrifuging to obtain Cu 2 O @ CuS @ composite structure;
the Cu is added 2 Dispersing an O @ CuS @ composite structure and a nickel cobalt source in an ethanol/deionized water mixed solution to obtain a mixed solution B, adding polyvinylpyrrolidone into the mixed solution B and stirring,obtaining a mixed solution C;
and (3) dripping a sodium thiosulfate pentahydrate solution into the mixed solution C for reaction, centrifuging, collecting precipitates, washing and drying to obtain the CuS @ NiCo LDH core-shell composite material.
In a second aspect of the invention, a CuS @ NiCo LDH core-shell composite material obtained by the method is provided.
In a third aspect of the invention, the application of the CuS @ NiCo LDH core-shell composite material as an electrocatalyst is provided.
One or more technical solutions in the embodiments of the present invention have at least the following technical effects or advantages:
(1) The invention provides a preparation method of a CuS @ NiCo LDH core-shell composite material, which utilizes cubic Cu 2 And O is used as a template, and the nano hollow CuS @ NiCo LDH core-shell composite cube is prepared for the first time by adopting vulcanization and combining with an etching and deposition path. The method is simple and easy to operate, short in reaction period, environment-friendly and low in cost.
(2) The CuS @ NiCo LDH composite material prepared by the method has the advantages of uniform particle size, stable structure and reliable performance. The two-dimensional LDH nanosheets on the outer layer can increase the contact area between the catalyst and the electrolyte, capture more charges in the glucose oxidation reaction and facilitate the electrocatalytic oxidation-reduction reaction of adsorbed molecules on the surface of the electrode; the internal CuS can be used as a current collector to improve electron transfer in catalytic reaction. The design of the nano hollow CuS @ NiCo LDH core-shell composite structure is beneficial to the two-dimensional material to adjust the electronic structure, accelerate the electron transfer and improve the electrocatalytic activity; meanwhile, the conductive CuS bears the supporting effect in the whole nano system, so that the agglomeration of NiCo LDH nano sheets is avoided, the contact area between an electrolyte and electrodes is increased, the electron transfer rate is improved, and the rapid glucose response current is caused. Such electrocatalysts have significant electrocatalytic activity.
Drawings
In order to more clearly illustrate the technical solutions in the embodiments of the present invention, the drawings needed to be used in the description of the embodiments are briefly introduced below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and it is obvious for those skilled in the art to obtain other drawings based on the drawings without creative efforts.
FIG. 1 shows Cu used in example 1 of the present invention 2 A Field Emission Scanning Electron Microscope (FESEM) image of the O template with a resolution of 1 μm;
FIG. 2 (a) shows a low power scanning electron microscope (FESEM) image of CuS @ NiCo LDH nanoparticles prepared in example 1 of the present invention with a resolution of 10 μm; FIG. 2 (b) shows a high power scanning electron microscope (FESEM) image of CuS @ NiCo LDH nanoparticles prepared in example 1 of the present invention with a resolution of 500nm;
FIG. 3 shows a Transmission (TEM) electron micrograph of CuS @ NiCo LDH nanoparticles prepared in example 1 of the present invention with a resolution of 500nm;
FIG. 4 shows the results of electrochemical detection of glucose by CuS @ NiCo LDH modified electrode in example 1 of the present invention: wherein the solid line is the cyclic voltammogram of the CuS @ NiCo LDH modified electrode in sodium hydroxide solution (0.1M) containing 1mM glucose, and the dotted line is CuS @ Ni (OH) 2 Cyclic voltammograms of the modified electrodes in sodium hydroxide solution (0.1M) without glucose.
Detailed Description
The present invention will be described in detail below with reference to specific embodiments and examples, and the advantages and various effects of the present invention will be more clearly apparent therefrom. It will be understood by those skilled in the art that these specific embodiments and examples are for the purpose of illustrating the invention and are not to be construed as limiting the invention.
Throughout the specification, unless otherwise specifically noted, terms used herein should be understood as having meanings as commonly used in the art. Accordingly, unless defined otherwise, 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. If there is a conflict, the present specification will control.
Unless otherwise specifically stated, various raw materials, reagents, instruments, equipment and the like used in the present invention are commercially available or can be obtained by existing methods.
In order to solve the technical problems, the general idea of the embodiment of the application is as follows:
according to a typical embodiment of the present invention, there is provided a method for preparing a cus@ nico LDH core-shell composite material, the method including:
s1, adding Cu 2 Dispersing the O in an ethanol/deionized water mixed solution, and performing ultrasonic treatment to obtain a mixed solution A; then dropwise adding a sodium sulfide solution into the mixed solution A for reaction, and centrifuging to obtain Cu 2 O @ CuS @ composite structure;
in the step S1, the first step is performed,
the nickel-cobalt source is a nickel source and a cobalt source, the nickel source is selected from one of nickel chloride, nickel nitrate and nickel sulfate, and the cobalt source is selected from one of cobalt chloride, cobalt nitrate and cobalt sulfate.
Obtaining the Cu in the mixed solution A 2 The mass volume ratio of O and ethanol/deionized water is (1-3) mg: (1-3) ml; preferably 1mg:1ml.
The volume ratio of the ethanol to the deionized water in the ethanol/deionized water mixed solution is (1-2): (1-2).
The volume ratio of the mixed solution A to the sodium sulfide solution is 100: and 3, the concentration range of the sodium sulfide solution is 0.01-0.1M.
S2, mixing the Cu 2 Dispersing an O @ CuS @ composite structure and a nickel cobalt source in an ethanol/deionized water mixed solution to obtain a mixed solution B, adding polyvinylpyrrolidone into the mixed solution B, and stirring to obtain a mixed solution C;
in the step S2, the first step is performed,
the Cu 2 The mass ratio of the O @ CuS @ composite structure to the nickel-cobalt source is 10: (3-4); preferably 10:3.6.
the Cu 2 The mass-volume ratio of the O @ CuS @ composite structure to the ethanol/deionized water mixed solution is (1-3) mg: (1-3) ml; preferably 1mg:1ml.
The volume mass ratio of the mixed solution B to the polyvinylpyrrolidone is 10 (ml): 1 (mg).
And S3, dripping a sodium thiosulfate pentahydrate solution into the mixed solution C for reaction, centrifuging, collecting the precipitate, washing and drying to obtain the CuS @ NiCo LDH core-shell composite material.
The volume ratio of the sodium thiosulfate pentahydrate solution to the mixed solution C is 4:10, and the concentration of the sodium thiosulfate pentahydrate solution is 0.1-1M.
According to another exemplary embodiment of the invention, the CuS @ NiCo LDH core-shell composite material obtained by the method is provided.
According to another exemplary embodiment of the invention, the use of the CuS @ NiCo LDH core-shell composite material as an electrocatalyst is provided.
The following will explain in detail a CuS @ NiCo LDH core-shell composite material of the present application, its preparation method and application in combination with examples, comparative examples and experimental data.
Example 1
The preparation method of the CuS @ NiCo LDH core-shell composite cube is simple to operate and easy to control, and comprises the following specific steps of:
1. weighing a certain amount of 100mg Cu 2 Dispersing the O cubic model in 100ml ethanol/deionized water mixed solution (volume ratio 1:1), and carrying out ultrasonic treatment for 10 minutes; dropwise adding 3mL of sodium sulfide solution (0.086M) into the solution, reacting for 30 seconds, and then centrifugally collecting to obtain Cu 2 O @ CuS composite structure;
2. the above precipitate was re-dispersed in 100ml of ethanol/deionized water mixed solution, 3.3g of polyvinylpyrrolidone (Mw =40,000), 10mg of nickel chloride hexahydrate, and 20mg of cobalt chloride hexahydrate were added, and magnetically stirred for 30 minutes;
3. 40mL of a sodium thiosulfate pentahydrate solution (1M) was slowly dropped into the above solution, reacted for 3 hours, and then collected by centrifugation. And finally, washing the centrifuged sample by using water, ethanol/deionized water mixed solution and ethanol for 5 times in sequence, and drying in an oven to obtain the CuS @ NiCo LDH core-shell composite cubic structure.
Example 2
1. Weighing a certain amount of 100mg Cu 2 Dispersing the O cubic template in 100ml ethanol/deionized water mixed solution (volume ratio is 1:1), and performing ultrasonic treatment for 10 minutes; dropwise adding 3mL of sodium sulfide solution (0.086M) into the solution, reacting for 30 seconds, and centrifugally collecting to obtainCu 2 O @ CuS composite structure;
2. the above precipitate was re-dispersed in 100ml of ethanol/deionized water mixed solution, 3.3g of polyvinylpyrrolidone (Mw =40,000), 15mg of nickel chloride hexahydrate, and 15mg of cobalt chloride hexahydrate were added, and magnetically stirred for 30 minutes;
3. 40mL of a sodium thiosulfate pentahydrate solution (1M) was slowly dropped into the above solution, reacted for 3 hours, and then collected by centrifugation. And finally, washing the centrifuged sample by using water, ethanol/deionized water mixed solution and ethanol for 5 times in sequence, and drying in an oven to obtain the CuS @ NiCo LDH core-shell composite cubic structure.
Example 3
1. Weighing a certain amount of 100mg Cu 2 Dispersing an O cubic template in 100ml of ethanol/deionized water mixed solution (the volume ratio is 1:1), and carrying out ultrasonic treatment for 10 minutes; dropwise adding 3mL of sodium sulfide solution (0.086M) into the solution, reacting for 30 seconds, and centrifugally collecting to obtain Cu 2 O @ CuS composite structure;
2. the precipitate was re-dispersed in 100ml of an ethanol/deionized water mixed solution, 3.3g of polyvinylpyrrolidone (Mw =40,000), 20mg of nickel chloride hexahydrate, and 10mg of cobalt chloride hexahydrate were added, and magnetic stirring was performed for 30 minutes;
3. 40mL of a sodium thiosulfate pentahydrate solution (1M) was slowly dropped into the above solution, reacted for 3 hours, and then collected by centrifugation. And finally, washing the centrifuged sample with water, ethanol/deionized water mixed liquor and ethanol for 5 times in sequence, and drying in an oven to obtain the CuS @ NiCo LDH core-shell composite cubic structure.
Example 4
1. Weighing a certain amount of 100mg Cu 2 Dispersing the cubic template in 100ml ethanol/deionized water mixed solution (volume ratio 1:1), and carrying out ultrasonic treatment for 5 minutes; 5mL of sodium sulfide solution (0.086M) was added dropwise to the above solution, reacted for 30 seconds, and then centrifuged to obtain Cu 2 O @ CuS composite structure;
2. the precipitate was re-dispersed in 100ml of an ethanol/deionized water mixed solution, 3.3g of polyvinylpyrrolidone (Mw =40,000), 10mg of nickel nitrate hexahydrate, and 20mg of cobalt nitrate hexahydrate were added, and magnetic stirring was performed for 30 minutes;
3. 40mL of a sodium thiosulfate pentahydrate solution (1M) was slowly dropped into the above solution, reacted for 3 hours, and then collected by centrifugation. And finally, washing the centrifuged sample with water, ethanol/deionized water mixed liquor and ethanol for 5 times in sequence, and drying in an oven to obtain the CuS @ NiCo LDH core-shell composite cubic structure.
Experimental example 1
1. Scanning electron microscope and transmission electron microscope characterization
(1) Cu used in the invention 2 The scanning electron micrograph of the O-template is shown in fig. 1, exhibiting a fine and stable cubic morphology;
(2) The low-power and high-power scanning electron micrographs of the CuS @ NiCo LDH core-shell composite material prepared in the embodiment 1 of the invention are respectively shown in FIGS. 2a-b, and it can be seen that the CuS @ NiCo LDH core-shell composite material prepared in the invention has the structural morphology and the Cu 2 The O template has consistent shape, uniform material size which is about 500nm, stable structure, uniform dispersion and no agglomeration, and the surface of the outer functional shell is formed by gathering extremely thin nano sheets to form an ideal two-dimensional network structure.
(3) The transmission electron microscope picture of the CuS @ NiCo LDH core-shell composite material prepared in the embodiment 1 of the invention is shown in FIG. 3, and it can be known from the picture that the CuS @ NiCo LDH core-shell composite material prepared in the invention is a multi-stage hollow cubic structure, the inner layer CuS and the outer layer NiCo LDH are tightly combined without gap, and a functional shell with the thickness of about 70nm is formed.
2. Specific surface area and porosity determination
The core-shell composite hollow structure not only improves the electron collection rate of the active material, obtains a large number of catalytic active sites and realizes rapid oxidation-reduction reaction, but also improves the specific surface area and the porosity, and the specific surface area reaches 89.3m 2 g -1 The porosity reaches 0.68m 3 g -1 This is advantageous in limiting the electron transport path and promoting diffusion kinetics of ions.
3. Electrocatalytic application
The CuS hollow structure is used as the support of the two-dimensional NiCo LDH, so that the conductivity of the composite material is obviously improved, and the electrocatalytic behavior of the NiCo LDH shell in the reaction is not interfered.
The electrocatalytic response of the CuS @ NiCo LDH core-shell composite material prepared in the embodiment 1 of the invention to glucose comprises the following steps: (1) Performing cyclic voltammetry scanning in 0.1M sodium hydroxide solution by using an electrochemical workstation, and recording a scanning curve; (2) Dripping 1mM glucose into the solution, continuing to perform cyclic voltammetry scanning, and recording a scanning curve; (3) And comparing the peak value change of the oxidation peak before and after the glucose is added, wherein the changed value is the glucose catalytic current.
The result is shown in FIG. 4, after 1mM glucose is added, the glucose response current reaches 45 μ A, which fully proves that the CuS @ NiCo LDH core-shell composite material prepared by the invention has great potential in electrocatalysis application.
Finally, it should also be noted that the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus.
While preferred embodiments of the present invention have been described, additional variations and modifications in those embodiments may occur to those skilled in the art once they learn of the basic inventive concepts. Therefore, it is intended that the appended claims be interpreted as including preferred embodiments and all such alterations and modifications as fall within the scope of the invention.
It will be apparent to those skilled in the art that various changes and modifications may be made in the present invention without departing from the spirit and scope of the invention. Thus, if such modifications and variations of the present invention fall within the scope of the claims of the present invention and their equivalents, the present invention is also intended to include such modifications and variations.
Claims (10)
1. A preparation method of a CuS @ NiCo LDH core-shell composite material is characterized by comprising the following steps:
mixing Cu 2 Dispersing the O in the ethanol/deionized water mixed solution, and performing ultrasonic treatment to obtain a mixed solution A; then dropwise adding a sodium sulfide solution into the mixed solution A for reaction, and separatingHeart, obtaining Cu 2 O @ CuS @ composite structure;
the Cu is added 2 Dispersing an O @ CuS @ composite structure and a nickel cobalt source in an ethanol/deionized water mixed solution to obtain a mixed solution B, adding polyvinylpyrrolidone into the mixed solution B, and stirring to obtain a mixed solution C;
and dripping a pentahydrate sodium thiosulfate solution into the mixed solution C for reaction, centrifuging, collecting the precipitate, washing and drying to obtain the CuS @ NiCo LDH core-shell composite material.
2. The method for preparing the CuS @ NiCo LDH core-shell composite material as claimed in claim 1, wherein the nickel-cobalt source is one selected from nickel chloride, nickel nitrate and nickel sulfate, and the cobalt source is one selected from cobalt chloride, cobalt nitrate and cobalt sulfate.
3. The method for preparing CuS @ NiCo LDH core-shell composite material as claimed in claim 1, wherein said obtaining Cu in mixed liquor A 2 The mass volume ratio of O and ethanol/deionized water is (1-3) mg: (1-3) ml.
4. The preparation method of the CuS @ NiCo LDH core-shell composite material as claimed in claim 1, wherein the volume ratio of ethanol to deionized water in the ethanol/deionized water mixed solution is (1-2): (1-2).
5. The method for preparing the CuS @ NiCo LDH core-shell composite material as claimed in claim 1, wherein the volume ratio of the mixed solution A to the sodium sulfide solution is 100:3, the concentration range of the sodium sulfide solution is 0.05-0.1M.
6. The method for preparing the CuS @ NiCo LDH core-shell composite material according to claim 1, wherein the Cu in the obtained mixed solution B 2 The mass ratio of the O @ CuS @ composite structure to the nickel-cobalt source is 10: (3-4).
7. The preparation method of the CuS @ NiCo LDH core-shell composite material as claimed in claim 1, wherein the volume-mass ratio of the mixed solution B to the polyvinylpyrrolidone is 10ml:1mg.
8. The method for preparing the CuS @ NiCo LDH core-shell composite material according to claim 1, wherein the volume ratio of the sodium thiosulfate pentahydrate solution to the mixed liquid C is 4:10, and the concentration of the sodium thiosulfate pentahydrate solution is 0.1-1M.
9. A cuss @ nico LDH core-shell composite material prepared by the method of any one of claims 1 to 8.
10. Use of the cus @ nico LDH core-shell composite material of claim 9 as electrocatalyst.
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| CN107824188A (en) * | 2017-10-27 | 2018-03-23 | 广西师范大学 | The preparation method of nickel cobalt layered double hydroxide/graphene elctro-catalyst |
| CN111960481A (en) * | 2020-09-04 | 2020-11-20 | 重庆文理学院 | A kind of Ni (OH)2Preparation method of @ CuS composite material |
| CN114917932A (en) * | 2022-05-12 | 2022-08-19 | 浙江师范大学 | For CO 2 Photoreduction synthesis of CO and H 2 Catalyst, preparation method and application |
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| CN107824188A (en) * | 2017-10-27 | 2018-03-23 | 广西师范大学 | The preparation method of nickel cobalt layered double hydroxide/graphene elctro-catalyst |
| CN111960481A (en) * | 2020-09-04 | 2020-11-20 | 重庆文理学院 | A kind of Ni (OH)2Preparation method of @ CuS composite material |
| CN114917932A (en) * | 2022-05-12 | 2022-08-19 | 浙江师范大学 | For CO 2 Photoreduction synthesis of CO and H 2 Catalyst, preparation method and application |
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