CN110721700A - Copper-cobalt-sulfur nanosheet array/molybdenum foil composite material, and preparation method and application thereof - Google Patents
Copper-cobalt-sulfur nanosheet array/molybdenum foil composite material, and preparation method and application thereof Download PDFInfo
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Abstract
The invention provides a copper-cobalt-sulfur nanosheet array/molybdenum foil composite material, a preparation method and application thereof2O4A nanosheet array of nanowires, followed by water as a solvent and thioacetamide as a sulfur source, to obtain CuCo composed of particles2S4The nanosheet array/molybdenum foil composite material effectively increases catalytic sites of the material, the contact area of an electrode material and an electrolyte and the conductivity of the material, so that the prepared copper-cobalt-sulfur nanosheet array/molybdenum foil composite material has good catalytic electrolysis water evolution hydrogen reaction performance. Compared with the prior art, the preparation process is simple, and the method is used for the electrolytic water hydrogen evolution reactionThe catalyst has excellent performance, can be used for catalyzing hydrogen evolution reaction in acid and alkaline environments, and has good practical application value.
Description
Technical Field
The invention relates to the field of micro-nano material preparation, in particular to CuCo2S4A nano-sheet array/molybdenum foil composite material, a preparation method and application thereof as a catalyst for an electrolysis water hydrogen evolution reaction.
Background
The use of fossil fuels in large quantities worldwide has brought about very serious environmental problems for many years. Such as haze, acid rain, continuously warmed global climate, etc., are associated with the long-term and high-volume use of fossil fuels. In addition, fossil fuels such as coal, natural gas and petroleum are difficult to regenerate in a short time, and are non-renewable energy sources, so that human beings inevitably face the problem of fossil fuel exhaustion in the near future. Therefore, the development of efficient, clean and renewable energy sources has become a priority in the scientific community of the twenty-first century.
Among the various renewable clean energy sources, hydrogen is one of the most promising candidates for the future replacement of traditional fossil fuels. The hydrogen has high combustion heat value and high energy density, only generates water after combustion, and has rich hydrogen element reserves on the earth. Hydrogen is a very excellent renewable clean energy source. However, the direct large-scale application of hydrogen as an energy source in practical life has many limitations, and how to effectively prepare hydrogen is an important problem to be solved.
In many current hydrogen production processes, pure hydrogen can be produced based on hydrogen evolution reaction occurring at the cathode of electrolyzed water. The hydrogen production by electrolyzing water has attracted great attention due to the advantages of simple and mild preparation conditions, easily obtained raw materials and the like. However, the over potential of the hydrogen evolution reaction causes the energy consumption of the hydrogen production process by water electrolysis to be too high, so that the practical use benefit is low, the practical application of the hydrogen production process by water electrolysis is limited, and the over potential of the hydrogen evolution reaction is reduced by a high-efficiency electrocatalyst.
At present, known high-efficiency hydrogen evolution reaction catalysts such as noble metals including Pt, Pd and the like have high price and limited reserves, which restricts the large-scale application of the catalysts to industrial production. Therefore, it is necessary to develop a material with high catalytic ability and low price to catalyze the hydrogen evolution reaction so as to realize the large-scale application of the hydrogen production process by water electrolysis.
In recent years, scientists find that the bonding energy of transition metal sulfide and hydrogen is similar to that of noble metal, theoretically, the transition metal sulfide has the performance of catalyzing hydrogen evolution reaction, and is an ideal material for replacing noble metal as an electro-catalysis hydrogen evolution reaction catalyst due to low price and rich reserves. However, bulk transition metal sulfides have a small specific surface area, few catalytically active sites, and low electron transport properties, and thus are not highly catalytic.
Disclosure of Invention
The invention aims to provide a copper-cobalt-sulfur nanosheet array/molybdenum foil composite material, wherein the copper-cobalt-sulfur nanosheet array formed by particles is synthesized on the surface of a molybdenum foil with excellent conductivity, so that the catalytic sites of the material, the contact area of an electrode material and an electrolyte and the conductivity of the material are effectively increased, and the prepared copper-cobalt-sulfur nanosheet array/molybdenum foil composite material has good catalytic electrolysis water-out hydrogen reaction performance.
The invention also aims to provide a preparation method of the copper-cobalt-sulfur nanosheet array/molybdenum foil composite material, which has the advantages of simple preparation process, easily available required materials, low price, simple experimental equipment and operating conditions, controllable reaction and easiness in large-scale production.
The invention also aims to provide an application of the copper-cobalt-sulfur nanosheet array/molybdenum foil composite material as a catalyst for an electrolytic water hydrogen evolution reaction.
The specific technical scheme of the invention is as follows:
a preparation method of a copper-cobalt-sulfur nanosheet array/molybdenum foil composite material comprises the following steps:
1) placing the molybdenum foil in the container containing Cu2+、Co2+Heating and reacting in a urea solution, taking out the molybdenum foil after the reaction is finished, and cleaning;
2) calcining the cleaned molybdenum foil in a muffle furnace to obtain CuCo2O4A composite of a nanosheet array/molybdenum foil;
3) the CuCo prepared in the step 2)2O4And (3) placing the nanosheet array/molybdenum foil composite material into a thioacetamide solution, heating for reaction, cooling to room temperature after the reaction is finished, taking out the molybdenum foil, washing and drying to obtain the copper-cobalt-sulfur nanosheet array/molybdenum foil composite material.
The Cu content in step 1)2+、Co2+And Cu in urea solution2+And Co2+In a molar ratio of 1: 1-1: 3;
the Cu content in step 1)2+、Co2+And Cu in urea solution2+The concentration of the urea is 0.01-0.03 mol/L, and the concentration of the urea is 0.06-0.1 mol/L.
The Cu content in step 1)2+、Co2+The preparation method of the solution of urea comprises the following steps: and dissolving copper salt, cobalt salt and urea in deionized water to obtain the catalyst.
The copper salt in the step 1) is any one of soluble copper salts containing crystal water or not containing crystal water; preferably copper chloride dihydrate, copper nitrate trihydrate or copper sulfate pentahydrate;
the cobalt salt in the step 1) is any one of soluble cobalt salts containing crystal water or not containing crystal water; preferably cobalt nitrate hexahydrate or cobalt chloride hexahydrate.
Further, the heating reaction conditions in the step 1) are as follows: heating and reacting for 5-8 h at a constant temperature of 80-120 ℃.
The calcination in the step 2) specifically comprises the following steps: calcining for 2-4 h in air at the temperature of 450-550 ℃;
the concentration of the thioacetamide solution in the step 3) is 0.06-0.1 mol/L. CuCo prepared by adopting method of the invention2O4And vulcanizing the nanosheet array/molybdenum foil material in the thioacetamide solution with the concentration, and obtaining a final product according to the reaction conditions of the invention.
The heating reaction conditions in the step 3) are as follows: heating and reacting for 8-12 h at a constant temperature of 170-200 ℃.
The invention provides a copper-cobalt-sulfur nanosheet array/molybdenum foil composite material, and the preparation method is adoptedObtaining CuCo composed of particles growing on the surface of the Mo foil2S4A nanosheet array material.
The invention provides an application of a copper-cobalt-sulfur nanosheet array/molybdenum foil composite material, and particularly relates to an application of the copper-cobalt-sulfur nanosheet array/molybdenum foil composite material as a catalyst for hydrogen evolution by water electrolysis.
CuCo prepared by the invention2S4The nano-sheet array/molybdenum foil composite material can be directly used as an electrode for catalyzing the electrolysis water hydrogen evolution reaction. The electrolytic water hydrogen evolution reaction is carried out at room temperature by using a standard three-electrode system. The prepared copper-cobalt-sulfur nanosheet array/molybdenum foil composite material is used as a working electrode, a carbon rod counter electrode and a saturated Ag/AgCl electrode are used as reference electrodes, and the electrolyte is 0.5M H2SO4The solution and a 1M KOH solution were subjected to a Linear Sweep Voltammetry (LSV) test at a sweep rate of 5 mV/s.
In the invention, urea, soluble cobalt salt and copper salt are heated and reacted at constant temperature, and under the condition of constant-temperature heating and reaction, the urea can be hydrolyzed to generate NH3Then NH3React with water to form OH-. In solution, OH-Co supplied with soluble cobalt and copper salts2+And Cu+2Reaction is carried out to generate a cobalt-copper precursor on the surface of the molybdenum foil. With the extension of the reaction time, the generated cobalt-copper precursor gradually grows into a one-dimensional nano structure and forms a lamellar layer, so that a nano sheet array structure formed by nano wires is formed on the surface of the molybdenum foil. By further calcination in air, the cobalt-copper precursor is converted to CuCo2O4To obtain CuCo2O4Nanosheet array/molybdenum foil composite. Prepared CuCo2O4CuCo in nanosheet array/molybdenum foil composite material2O4The nanosheets are hierarchical structures composed of nanowires, unlike typical single-structure nanosheets. Thereafter, water was used as a solvent and thioacetamide was used as a sulfur source. Under the constant-temperature heating environment of 170-200 ℃, thioacetamide dissolved in deionized water is gradually hydrolyzed, and sulfur ions are slowly released. The released sulfur ions form CuCo of the nano-sheet2O4Sulfurizing nano wire and substituting sulfur element for CuCo2O4The oxygen element in the solution is used to obtain CuCo2S4. In addition, because the sulfide ions are slowly released, the sulfidation reaction occurs first in CuCo2O4The surface of the material is gradually added with CuCo2O4Sulfurizing to CuCo2S4. This makes the original CuCo2O4The constituted nanosheet array structure is preserved, thereby obtaining CuCo constituted by particles2S4Nanosheet array/molybdenum foil composite.
Compared with binary sulfide, the ternary chalcogenide CuCo prepared by the method2S4Combines the advantages of Cu and Co metal sulfides, has good electrochemical performance and catalytic performance, and has performance advantages when being used as a catalyst for the electrolytic water hydrogen evolution reaction. CuCo prepared by the invention2S4The nano-sheets are composed of particles, and the specific surface area of the material is increased by the gaps among the particles, so that more catalytic active sites are provided. CuCo2S4The nano-sheets grow on the molybdenum foil substrate with good conductivity to form an array structure, so that the electron transmission rate in the hydrogen evolution reaction process can be improved, the contact area between the material and the electrolyte is increased, and the prepared CuCo2S4The nano-sheet array/molybdenum foil composite material can be directly used as an electrode for catalytic hydrogen evolution reaction. These advantages all greatly improve the prepared CuCo2S4The performance of hydrogen evolution reaction catalyzed by the nano-sheet array/molybdenum foil composite material.
Compared with the prior art, the copper-cobalt-sulfur nanosheet array/molybdenum foil composite material is prepared by a hydrothermal method, the preparation process is simple, the required materials are easy to obtain, the price is low, experimental equipment and operating conditions are simple, the reaction is controllable, and the large-scale production is easy to realize. Moreover, the molybdenum foil has good stability in acid and alkaline environments, so the CuCo prepared by the method has good stability2S4The nano-sheet array/molybdenum foil composite material can be used for catalyzing hydrogen evolution reaction in acidic and alkaline environments, and has good practical application value.
Drawings
The following describes embodiments of the present invention in further detail with reference to the accompanying drawings.
FIG. 1 shows the CuCo composed of nanowires obtained in example 12O4Scanning electron microscope images of the nanosheet array/molybdenum foil composite material;
FIG. 2 shows the CuCo composed of nanowires obtained in example 12O4The X-ray diffraction pattern of a sample stripped from the surface of the molybdenum foil is obtained after the nanosheet array/molybdenum foil composite material is subjected to ultrasonic treatment;
FIG. 3 is a graph of CuCo consisting of particles obtained in example 12S4Scanning electron microscope images of the nanosheet array/molybdenum foil composite material;
FIG. 4 is a graph of CuCo consisting of particles obtained in example 12S4The X-ray diffraction pattern of a sample stripped from the surface of the molybdenum foil is obtained after the nanosheet array/molybdenum foil composite material is subjected to ultrasonic treatment;
FIG. 5 is a graph of CuCo consisting of particles obtained in example 22S4A transmission electron microscope image of a sample stripped from the surface of the molybdenum foil is obtained after the nanosheet array/molybdenum foil composite material is subjected to ultrasonic treatment;
FIG. 6 is a CuCo composition of particles from example 32S4Scanning electron microscope images of the nanosheet array/molybdenum foil composite material;
FIG. 7 is a CuCo composition of particles from example 42S4Scanning electron microscope images of the nanosheet array/molybdenum foil composite material;
FIG. 8 is a graph of CuCo consisting of particles from example 52S4Scanning electron microscope images of the nanosheet array/molybdenum foil composite material;
FIG. 9 is a CuCo composition of particles from example 12S4Nanosheet array/molybdenum foil composite material and CuCo modified on molybdenum foil2S4The nano-sheet material and pure molybdenum foil are 0.5M H2SO4A comparison graph of polarization curves of catalytic hydrogen evolution reactions in solution;
FIG. 10 is a graph of CuCo consisting of particles obtained in example 12S4Nanosheet array/molybdenum foil composite material and CuCo modified on molybdenum foil2S4Nano sheet material,Polarization curves of pure molybdenum foils in a 1M KOH solution for catalytic hydrogen evolution reactions are shown.
Detailed Description
For the purpose of facilitating an understanding of the present invention, the present invention will now be described by way of examples. It should be understood by those skilled in the art that the examples are merely for the understanding of the present invention, and the specific description is illustrative and should not be construed as limiting the scope of the present invention. It will be appreciated by those skilled in the art that the present invention may be embodied in other specific forms without departing from the spirit or essential characteristics thereof, and it is therefore intended to cover all modifications within the scope of the invention or the equivalent thereof.
Example 1
A preparation method of a copper-cobalt-sulfur nanosheet array/molybdenum foil composite material comprises the following steps:
(1) respectively carrying out ultrasonic treatment on the molybdenum foil with the size of 1cm multiplied by 4cm for 5 minutes by using deionized water and ethanol to clean surface dirt, and then placing the cleaned molybdenum foil at 60 ℃ for vacuum drying for 5 hours for later use.
(2) Weighing 0.5mmol of cobalt nitrate hexahydrate, 0.5mmol of copper nitrate trihydrate and 2mmol of urea, sequentially adding the cobalt nitrate hexahydrate, the copper nitrate trihydrate and the urea into 30mL of deionized water, and stirring until the cobalt nitrate hexahydrate, the copper nitrate trihydrate and the urea are completely dissolved to obtain a uniform solution; transferring the solution into a high-pressure reaction kettle with a tetrafluoroethylene lining, putting the molybdenum foil treated in the step (1) into the solution, sealing the reaction kettle, putting the reaction kettle into a blast oven, and heating for 6 hours at a constant temperature of 100 ℃; after the reaction is finished, taking out the molybdenum foil to wash the molybdenum foil for 5 times by using deionized water and ethanol respectively;
(3) then, the molybdenum foil treated in the step (2) is placed into a muffle furnace and calcined for 4 hours in the air at the temperature of 450 ℃ to obtain CuCo consisting of nanowires2O4Nanosheet array/molybdenum foil composite.
(4) Weighing 2mmol of thioacetamide, adding the thioacetamide into 30mL of water, stirring until the thioacetamide is completely dissolved, transferring the solution into a reaction kettle with a polytetrafluoroethylene lining, and adding the CuCo prepared in the step (3)2O4Placing the nano-sheet array/molybdenum foil composite material into the solution, then sealing the reaction kettle, placing the reaction kettle into a blast oven, and keeping the temperature constant at 170 DEG CThe mixture is heated for 12 hours.
(5) And after the reaction is finished, naturally cooling to room temperature, taking out the molybdenum foil in the reaction kettle, respectively cleaning the molybdenum foil for 5 times by using deionized water and ethanol, and then drying for 8 hours in a vacuum drying oven at the temperature of 60 ℃ to obtain the product.
Fig. 1 is a scanning electron microscope image of the product obtained in step (3) of example 1, which shows that the product is a nanosheet array/molybdenum foil composite material composed of nanowires.
FIG. 2 is an X-ray diffraction pattern of a sample peeled from the surface of a molybdenum foil obtained by subjecting the product obtained in the step (3) of example 1 to ultrasonication, in which the positions of diffraction peaks are correlated with CuCo2O4The powder X-ray diffraction standard card JCPDSNo.78-2177 is inosculated, which shows that the nano-sheet composed of the nano-wires on the surface of the molybdenum foil is CuCo2O4。
Fig. 3 is a scanning electron microscope image of the product obtained in step (5) of example 1, which shows that the product is a nanosheet array/molybdenum foil composite material composed of particles.
FIG. 4 is an X-ray diffraction pattern of a sample peeled from the surface of a molybdenum foil obtained by subjecting the product obtained in the step (5) of example 1 to ultrasonication, in which the positions of diffraction peaks are correlated with CuCo2S4The powder X-ray diffraction standard card JCPDS No.09-0233 is in agreement. The nano-sheet composed of particles on the surface of the molybdenum foil is copper-cobalt-sulfur, and the final product is CuCo composed of particles2S4Nanosheet array/molybdenum foil composite.
Example 2
A preparation method of a copper-cobalt-sulfur nanosheet array/molybdenum foil composite material comprises the following steps:
(1) respectively carrying out ultrasonic treatment on the molybdenum foil with the size of 1cm multiplied by 4cm by deionized water and ethanol for 5 minutes to clean surface dirt, and then carrying out vacuum drying on the cleaned molybdenum foil for 5 hours at the temperature of 60 ℃ for later use.
(2) Weighing 1mmol of cobalt nitrate hexahydrate, 0.5mmol of copper nitrate trihydrate and 3mmol of urea, sequentially adding the cobalt nitrate hexahydrate, the 0.5mmol of copper nitrate trihydrate and the 3mmol of urea into 50mL of deionized water, and stirring until the cobalt nitrate, the 0.5mmol of copper nitrate trihydrate and the 3mmol of urea are completely dissolved to obtain a uniform solution; transferring the solution to a high-pressure reaction kettle with a tetrafluoroethylene lining, putting the molybdenum foil treated in the step (1) into the solution, sealing the reaction kettle, putting the reaction kettle into a blast oven, and heating for 5 hours at a constant temperature of 120 ℃; after the reaction is finished, taking out the molybdenum foil to wash the molybdenum foil for 5 times by using deionized water and ethanol respectively;
(3) then, the molybdenum foil treated in the step (2) is placed into a muffle furnace and calcined for 3 hours at the temperature of 500 ℃ in the air to obtain CuCo consisting of nanowires2O4Nanosheet array/molybdenum foil composite.
(4) Weighing 3mmol of thioacetamide, adding the thioacetamide into 50mL of water, stirring until the thioacetamide is completely dissolved, transferring the solution into a reaction kettle with a polytetrafluoroethylene lining, and adding the CuCo prepared in the step (3)2O4And (3) placing the nano sheet array/molybdenum foil composite material into a thioacetamide solution, then sealing the reaction kettle, placing the reaction kettle into a blast oven, and heating for 10 hours at a constant temperature of 190 ℃.
(5) After the reaction is finished, naturally cooling to room temperature, taking out the molybdenum foil in the reaction kettle, respectively cleaning the molybdenum foil for 5 times by using deionized water and ethanol, and then placing the molybdenum foil in a vacuum drying oven for drying for 8 hours at the temperature of 60 ℃ to obtain a CuCo product consisting of particles2S4Nanosheet array/molybdenum foil composite.
Fig. 5 is a transmission electron microscope image of a sample obtained after the product obtained in the step (5) of example 2 is subjected to ultrasonic wave, and the sample is ultrasonically peeled from the surface of the molybdenum foil, which shows that the nanosheets on the surface of the molybdenum foil are composed of particles.
Example 3
A preparation method of a copper-cobalt-sulfur nanosheet array/molybdenum foil composite material comprises the following steps:
(1) respectively carrying out ultrasonic treatment on the molybdenum foil with the size of 2cm multiplied by 4cm by deionized water and ethanol for 5 minutes respectively to clean the dirt on the surface, and then carrying out vacuum drying on the cleaned molybdenum foil for 5 hours at the temperature of 60 ℃ for later use.
(2) Weighing 4.5mmol of cobalt nitrate hexahydrate, 1.5mmol of copper nitrate trihydrate and 5mmol of urea, sequentially adding the materials into 50mL of deionized water, and stirring until the three materials are completely dissolved to obtain a uniform solution; transferring the solution into a high-pressure reaction kettle with a tetrafluoroethylene lining, placing the molybdenum foil treated in the step (1) into the solution, sealing the reaction kettle, placing the reaction kettle into a blast oven, and heating for 8 hours at a constant temperature of 80 ℃; after the reaction is finished, taking out the molybdenum foil to wash the molybdenum foil for 5 times by using deionized water and ethanol respectively;
(3) and (3) putting the molybdenum foil treated in the step (2) into a muffle furnace, calcining for 2 hours at 550 ℃ in air to obtain CuCo consisting of nanowires2O4Nanosheet array/molybdenum foil composite.
(4) Weighing 5mmol of thioacetamide, adding the thioacetamide into 50mL of water, stirring until the thioacetamide is completely dissolved, transferring the solution into a reaction kettle with a polytetrafluoroethylene lining, and adding the CuCo prepared in the step (3)2O4And (3) placing the nano-sheet array/molybdenum foil composite material into a thioacetamide solution, then sealing the reaction kettle, placing the reaction kettle into a blast oven, and heating for 8 hours at a constant temperature of 200 ℃.
(5) After the reaction is finished, naturally cooling to room temperature, taking out the molybdenum foil in the reaction kettle, respectively washing the molybdenum foil for 5 times by using deionized water and ethanol, placing the molybdenum foil in a vacuum drying oven at 60 ℃, and drying for 8 hours to obtain a CuCo product consisting of particles2S4Nanosheet array/molybdenum foil composite.
FIG. 6 shows that the CuCo particles obtained in step (5) of example 3 are CuCo particles2S4Scanning electron microscope images of the nanosheet array/molybdenum foil composite.
Example 4
A preparation method of a copper-cobalt-sulfur nanosheet array/molybdenum foil composite material comprises the following steps:
(1) respectively carrying out ultrasonic treatment on the molybdenum foil with the size of 1cm multiplied by 4cm by deionized water and ethanol for 5 minutes to clean surface dirt, and then carrying out vacuum drying on the cleaned molybdenum foil for 5 hours at the temperature of 60 ℃ for later use.
(2) Weighing 1mmol of cobalt chloride hexahydrate, 0.5mmol of copper chloride dihydrate and 3mmol of urea, sequentially adding the cobalt chloride hexahydrate, the 0.5mmol of copper chloride dihydrate and the 3mmol of urea into 30mL of deionized water, and stirring until the cobalt chloride, the copper chloride dihydrate and the urea are completely dissolved to obtain a uniform solution; transferring the solution into a high-pressure reaction kettle with a tetrafluoroethylene lining, placing the molybdenum foil treated in the step (1) into the solution, sealing the reaction kettle, placing the reaction kettle into a blast oven, and heating for 5 hours at a constant temperature of 120 ℃; after the reaction is finished, taking out the molybdenum foil to wash the molybdenum foil for 5 times by using deionized water and ethanol respectively;
(3) then the step (2) is performedPlacing the treated molybdenum foil into a muffle furnace, calcining for 4 hours at 450 ℃ in air to obtain CuCo consisting of nanowires2O4Nanosheet array/molybdenum foil composite.
(4) Weighing 2mmol of thioacetamide, adding the thioacetamide into 30mL of water, stirring until the thioacetamide is completely dissolved, transferring the solution into a reaction kettle with a polytetrafluoroethylene lining, and adding the CuCo prepared in the step (3)2O4And (3) putting the nano-sheet array/molybdenum foil composite material into a thioacetamide solution, then sealing the reaction kettle, putting the reaction kettle into a blast oven, and heating for 8 hours at a constant temperature of 200 ℃.
(5) After the reaction is finished, naturally cooling to room temperature, taking out the molybdenum foil in the reaction kettle, respectively cleaning the molybdenum foil for 5 times by using deionized water and ethanol, putting the molybdenum foil into a vacuum drying oven at 60 ℃, and drying for 8 hours to obtain a CuCo product consisting of particles2S4Nanosheet array/molybdenum foil composite.
FIG. 7 is a CuCo particle composition obtained in step (5) of example 42S4Scanning electron microscope images of the nanosheet array/molybdenum foil composite.
Example 5
A preparation method of a copper-cobalt-sulfur nanosheet array/molybdenum foil composite material comprises the following steps:
(1) respectively carrying out ultrasonic treatment on the molybdenum foil with the size of 2cm multiplied by 4cm by deionized water and ethanol for 5 minutes respectively to clean the dirt on the surface, and then carrying out vacuum drying on the cleaned molybdenum foil for 5 hours at the temperature of 60 ℃ for later use.
(2) Weighing 2mmol of cobalt nitrate hexahydrate, 1mmol of copper nitrate trihydrate and 4mmol of urea, sequentially adding the cobalt nitrate hexahydrate, the 1mmol of copper nitrate trihydrate and the 4mmol of urea into 50mL of deionized water, and stirring until the cobalt nitrate hexahydrate, the 1mmol of copper nitrate trihydrate and the 4mmol of urea are completely dissolved to obtain a uniform solution; transferring the solution into a high-pressure reaction kettle with a tetrafluoroethylene lining, placing the molybdenum foil dried in the step (1) into the solution, sealing the reaction kettle, placing the reaction kettle into a blast oven, and heating for 6 hours at a constant temperature of 100 ℃; after the reaction is finished, taking out the molybdenum foil, and washing the molybdenum foil with ethanol and deionized water for 5 times respectively;
(3) then, the molybdenum foil treated in the step (2) is placed into a muffle furnace and calcined for 3 hours at the temperature of 500 ℃ in the air to obtain CuCo consisting of nanowires2O4Nano-sheet arrayColumn/molybdenum foil composite.
(4) Weighing 4mmol of thioacetamide, adding the thioacetamide into 50mL of water, stirring until the thioacetamide is completely dissolved, transferring the solution into a reaction kettle with a polytetrafluoroethylene lining, and adding the CuCo prepared in the step (3)2O4And (3) putting the nano-sheet array/molybdenum foil composite material into a thioacetamide solution, then sealing the reaction kettle, putting the reaction kettle into a blast oven, and heating for 8 hours at a constant temperature of 200 ℃.
(5) After the reaction is finished, naturally cooling to room temperature, taking out the molybdenum foil in the reaction kettle, respectively cleaning the molybdenum foil for 5 times by using deionized water and ethanol, putting the molybdenum foil into a vacuum drying oven at 60 ℃, and drying for 8 hours to obtain a CuCo product consisting of particles2S4Nanosheet array/molybdenum foil composite.
FIG. 8 is a CuCo particle composition obtained in step (5) of example 52S4Scanning electron microscope images of the nanosheet array/molybdenum foil composite.
Example 6
An application of a copper-cobalt-sulfur nanosheet array/molybdenum foil composite material as a catalyst for hydrogen evolution from electrolyzed water is disclosed, and specifically, the property test of the reaction for hydrogen evolution from electrolyzed water as the catalyst is as follows:
the copper-cobalt-sulfur nanosheet array/molybdenum foil composite material obtained in example 1 was used for a catalytic electrolysis hydrogen evolution reaction. The electrolysis water hydrogen evolution reaction is carried out at room temperature by adopting a standard three-electrode system. The prepared copper-cobalt-sulfur nanosheet array/molybdenum foil composite material is directly used as a working electrode, a graphite rod is used as a counter electrode, a saturated Ag/AgCl electrode is used as a reference electrode, and the ratio of the total amount of the copper-cobalt-sulfur nanosheet array/molybdenum foil composite material to the total amount of the graphite rod is 0.5M H2SO4Linear Sweep Voltammetry (LSV) measurements were performed in solution or 1M KOH solution at a sweep rate of 5 mV/s.
For comparison, CuCo modified on molybdenum foil was also tested under the same conditions2S4The catalytic electrolysis hydro-evolution reaction performance of the nano sheet material and the pure molybdenum foil material without any material growing on the surface.
Single CuCo2S4The preparation method of the nano sheet material comprises the following steps:
(1) 2mmol of Co (NO)3)2·6H2O and 1mmol Cu (NO)3)2·3H2Adding O into 30mL of deionized water, and stirring for 10 minutes until the O and the deionized water are completely dissolved;
(2) 4mmol of thiourea was added to the solution obtained in the step (1), and after stirring for 15 minutes, 2mL of ethylenediamine was further added thereto and stirred uniformly.
(3) Transferring the solution into a reaction kettle with a polytetrafluoroethylene lining, sealing the reaction kettle, putting the reaction kettle into a blast oven, and heating for 12 hours at a constant temperature of 200 ℃.
(4) After the reaction is finished, naturally cooling to room temperature, centrifugally separating out black products in the reaction kettle, respectively washing the molybdenum foil for 5 times by using deionized water and ethanol, putting the molybdenum foil into a vacuum drying oven at 60 ℃, and drying for 8 hours to obtain CuCo2S4A nanosheet material.
Single CuCo2S4The preparation method of the nano-sheet material is based on the method reported in the document ACS Catalysis, 2017, 7, 5871-5879. The literature reports that CuCo prepared by the method is proved2S4The nanosheet material is of a complete lamellar structure, rather than CuCo consisting of particles prepared by the method2S4A nanosheet structure.
The prepared single CuCo2S4The nanosheet material is further modified on the surface of the molybdenum foil and used for testing the reaction performance of the electrolysis water hydrogen evolution, and the modification method comprises the following steps:
(1) respectively carrying out ultrasonic treatment on the molybdenum foil with the size of 1cm multiplied by 4cm by deionized water and ethanol for 5 minutes to clean surface dirt, and then carrying out vacuum drying on the cleaned molybdenum foil for 5 hours at the temperature of 60 ℃ for later use.
(2) Taking 5mg of prepared single CuCo2S4Nanosheet material, and 20 μ L of Nafion (5 wt%) solution, which was added sequentially to 1mL of isopropanol, and the solution was sonicated for 30 minutes to give a uniformly dispersed suspension.
(3) 0.6mL of the suspension is uniformly dripped on the surface of the treated and cleaned molybdenum foil, and then the molybdenum foil is dried for 6 hours in vacuum at 40 ℃ to obtain CuCo modified on the molybdenum foil2S4A nanosheet material.
The method comprises the following steps of (1) carrying out pretreatment on a pure molybdenum foil material with no material growing on the surface: respectively carrying out ultrasonic treatment on the molybdenum foil with the size of 1cm multiplied by 4cm by deionized water and ethanol for 5 minutes to clean surface dirt, and then carrying out vacuum drying on the cleaned molybdenum foil for 5 hours at the temperature of 60 ℃ for later use.
The CuCo modified on molybdenum foil prepared in the way is2S4Nanosheet material, pure molybdenum foil material with no material grown on surface and CuCo consisting of particles prepared by the method2S4The nano-sheet array/molybdenum foil composite material is improved and compared:
FIG. 9 is at 0.5M H2SO4Copper-cobalt-sulfur nanosheet array/molybdenum foil composite material obtained in example 1 in solution, and CuCo modified on molybdenum foil2S4And (3) comparing polarization curves of the catalytic hydrogen evolution reaction of the nanosheet material and the pure molybdenum foil material. The figure shows that the pure molybdenum foil material only shows weak performance of catalyzing hydrogen evolution reaction in an acid environment, and the current density reaches 10mA/cm2The overpotential required was 369 mV. CuCo modified on molybdenum foil compared with pure molybdenum foil2S4The catalytic hydrogen evolution reaction performance of the nanosheet material is improved, and the current density reaches 10mA/cm2The overpotential is 258 mV. The copper-cobalt-sulfur nanosheet array/molybdenum foil composite material synthesized by the method has good catalytic hydrogen evolution reaction performance, and the current density reaches 10mA/cm2The overpotential is 134 mV.
FIG. 10 shows the copper-cobalt-sulfur nanosheet array/molybdenum foil composite material obtained in example 1, CuCo modified on molybdenum foil in 1M KOH solution2S4And (3) comparing polarization curves of the catalytic hydrogen evolution reaction of the nanosheet material and the pure molybdenum foil material. The figure shows that the pure molybdenum foil material still only shows weak performance of catalyzing hydrogen evolution reaction in alkaline environment, and the current density reaches 10mA/cm2The overpotential required was 365 mV. CuCo modified on molybdenum foil in alkaline environment2S4The catalytic hydrogen evolution reaction performance of the nanosheet material is also weak, and the current density reaches 10mA/cm2The overpotential was 307 mV. The copper-cobalt-sulfur nanosheet array/molybdenum foil composite material synthesized by the method still can show good catalytic hydrogen evolution reaction performance, and the current density reaches 10mA/cm2The overpotential was 152 mV.
Test results show that the copper-cobalt-sulfur nanosheet array/molybdenum foil composite material prepared by the method disclosed by the invention shows good hydrogen evolution reaction catalytic activity in acidic and alkaline environments, and has a good practical application value.
Claims (9)
1. A preparation method of a copper-cobalt-sulfur nanosheet array/molybdenum foil composite material is characterized by comprising the following steps:
1) placing the molybdenum foil in the container containing Cu2+、Co2+Heating and reacting in a urea solution, taking out the molybdenum foil after the reaction is finished, and cleaning;
2) calcining the cleaned molybdenum foil in a muffle furnace to obtain CuCo2O4A composite of a nanosheet array/molybdenum foil;
3) the CuCo prepared in the step 2)2O4And (3) placing the nanosheet array/molybdenum foil composite material into a thioacetamide solution, heating for reaction, cooling to room temperature after the reaction is finished, taking out the molybdenum foil, washing and drying to obtain the copper-cobalt-sulfur nanosheet array/molybdenum foil composite material.
2. The method according to claim 1, wherein the Cu is contained in the step 1)2+、Co2+And Cu in urea solution2+And Co2+In a molar ratio of 1: 1-1: 3.
3. the production method according to claim 1 or 2, wherein the Cu is contained in step 1)2+、Co2+And Cu in urea solution2+The concentration of the urea is 0.01-0.03 mol/L, and the concentration of the urea is 0.06-0.1 mol/L.
4. The method according to claim 1, wherein the heating reaction in step 1) is carried out under the following conditions: heating and reacting for 5-8 h at a constant temperature of 80-120 ℃.
5. The method according to claim 1 or 4, characterized in that the calcination in step 2) is in particular: calcining for 2-4 hours in air at the temperature of 450-550 ℃.
6. The method according to claim 1, wherein the concentration of the thioacetamide solution in step 3) is 0.06-0.1 mol/L.
7. The production method according to claim 1, wherein the conditions of the heating reaction in step 3) are: heating and reacting for 8-12 h at a constant temperature of 170-200 ℃.
8. The copper-cobalt-sulfur nanosheet array/molybdenum foil composite material prepared by the preparation method of any one of claims 1 to 7, wherein the copper-cobalt-sulfur nanosheet array/molybdenum foil composite material is formed by growing CuCo consisting of particles on the surface of a Mo foil2S4A nanosheet array material.
9. The application of the copper-cobalt-sulfur nanosheet array/molybdenum foil composite material prepared by the preparation method of any one of claims 1 to 7 is characterized by being applied as a catalyst for hydrogen evolution by water electrolysis.
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| CN113846349A (en) * | 2021-09-28 | 2021-12-28 | 安徽师范大学 | Co-doped molybdenum selenide nanosheet/Mo foil composite material, preparation method and application thereof |
| CN115440503A (en) * | 2022-08-22 | 2022-12-06 | 桂林电子科技大学 | Cobalt copper sulfide nanosheet and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN113846349A (en) * | 2021-09-28 | 2021-12-28 | 安徽师范大学 | Co-doped molybdenum selenide nanosheet/Mo foil composite material, preparation method and application thereof |
| CN113846349B (en) * | 2021-09-28 | 2023-02-21 | 安徽师范大学 | Co-doped molybdenum selenide nanosheet/Mo foil composite material, preparation method and application thereof |
| CN115440503A (en) * | 2022-08-22 | 2022-12-06 | 桂林电子科技大学 | Cobalt copper sulfide nanosheet and preparation method thereof |
| CN115440503B (en) * | 2022-08-22 | 2023-05-12 | 桂林电子科技大学 | Cobalt copper sulfide nanosheets and preparation method thereof |
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