CN113279005A - Cobalt doped MoS2/NiS2Preparation method of porous heterostructure material and application of material in electrocatalytic hydrogen evolution - Google Patents
Cobalt doped MoS2/NiS2Preparation method of porous heterostructure material and application of material in electrocatalytic hydrogen evolution Download PDFInfo
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Abstract
The invention belongs to the technical field of composite material preparation, and relates to cobalt-doped MoS2/NiS2A preparation method of a porous heterostructure material. The invention takes the conductive carbon cloth as a functional substrate, and NiS uniformly grows on activated carbon cloth fibers through a series of hydrothermal, calcining and solvothermal reactions2Nanosheets; with NiS2The sulfur atom of the nano-sheet is 'seed', NiS2The 2D structure of the nano-sheet is a framework in NiS2Synchronous growth of MoS on nano-chips2Nanosheet and cobalt doping to obtain cobalt doping、MoS2NiS wrapped by nano-microspheres2A porous heterostructure. The invention prepares Co-MoS from bottom to top2/NiS2CC, simple and controllable operation process and high product load rate; catalyst consisting of NiS2Supported by nanosheets, grown in NiS2Co-doped MoS on nanosheets2Nanosheet, 2D NiS2The nano-sheet has high specific surface area and conductivity, can enhance the electron transmission efficiency, improve the dispersibility of the catalyst and accelerate the basic reaction of the water cracking step. The method has the advantages of simple process, relatively mild conditions, high catalyst yield, low production cost and the like, and can be used for large-scale production.
Description
Technical Field
The invention belongs to the technical field of composite material preparation, relates to a catalyst for hydrogen evolution by electrolysis and water, and particularly relates to cobalt-doped MoS2/NiS2A preparation method of a porous heterostructure material and application of the material in electrocatalytic hydrogen evolution are provided.
Background
The extreme change of the climate environment and the energy crisis problem are accompanied with the development process of human industrialization, and hydrogen energy has the advantages of zero carbon emission, reproducibility, high energy density and the like, and is beneficial to improving the energy utilization efficiency. The hydrogen source is wide, and the preparation forms are various, such as coal hydrogen production, natural gas hydrogen production, methanol hydrogen production, water electrolysis hydrogen production and the like. Because of abundant water resources on the earth, the hydrogen production process is environment-friendly, the method is simple, and the water electrolysis is the most ideal hydrogen production mode. However, compared with theoretical deduction, various resistances exist in the actual electrolysis process, such as electrolyte resistance, contact resistance of an electrode and a water molecule interface, resistance of hydrogen produced by an electrode interface to the electrode interface, and the like, so that an overpotential higher than a theoretical value of 1.23V exists in the electrolysis potential, and the potential value is often higher than 1.8V. At present, the hydrogen production efficiency by water electrolysis is low, the reserves of the high-efficiency catalyst Pt and some noble metal oxides are rare, the power consumption cost is too high, and the method cannot be widely popularized and applied on an industrial scale. Therefore, transition metal catalytically active materials having a low overpotential have been widely studied.
The active components and the characteristic structure of the electrocatalyst are the main factors that determine its electrocatalytic efficiency. The selection of hydrogen evolution high-activity components is helpful for accelerating the water molecule cracking kinetic process and increasing the intermediate H*Adsorption sites, improved conductivity, etc. The structural design of the electrocatalytic material is varied, e.g. carbon layerThe coated core-shell structure, the hollow structure, the functional substrate load and the like, thereby achieving the purposes of protecting active substances, improving mass transfer efficiency, stability, conductivity and the like, and efficiently catalyzing and desorbing hydrogen. Of the plurality of transition metal catalytically active materials, 2D sheet-like hydrogen evolution active material MoS2Hydrogen adsorption is of interest because of its low energy and relative thermodynamic stability. However, pure MoS2The currently required electrocatalytic hydrogen evolution activity cannot be met due to low active site availability and poor electrical conductivity.
Previous studies have shown that MoS2Unsaturated sulfur atoms in the structure are the main catalytic active centers and are present in MoS in small parts2Unsaturated sulfur atom at the edge, and MoS2The large number of sulfur atoms on the basal surface is catalytically inactive, thereby hindering the electrocatalytic hydrogen evolution performance. In addition to that, MoS2Active sites are masked during growth and electrolysis due to the easy aggregation of van der waals forces present between adjacent layers. Thus, introducing a functional substrate promotes MoS2The conductivity and the dispersibility of the composite material are improved, the hydrogen release environment is improved, and the surface electronic state is adjusted by carrying out structural design, so that the composite material is an effective way for integrally making up the defects of the catalytic active material from multiple aspects.
Disclosure of Invention
In order to solve the defects of low catalytic efficiency, poor conductivity, easy aggregation in the growth and catalytic processes and the like in the hydrogen evolution process of the electrolyzed water catalytic active material, the invention discloses cobalt-doped MoS2/NiS2A preparation method of a porous heterostructure material.
Technical scheme
Cobalt-doped MoS2NiS wrapped by nano-microspheres2（Co-MoS2/NiS2The preparation method of/CC) porous heterostructure material uses conductive carbon cloth as substrate, firstly NiS uniformly grows on activated carbon cloth fiber through series of simple hydrothermal, calcining and solvothermal reactions2Nanosheets, further with NiS2The sulfur atom of the nano-sheet is 'seed', NiS2The 2D structure of the nano-sheet is a framework in NiS2Synchronous growth of MoS on nano-chips2Nanosheet and performingDoping with Co to obtain Co-doped MoS2NiS wrapped by nano-microspheres2A porous heterostructure material.
Cobalt-doped MoS2/NiS2（Co-MoS2/NiS2The preparation method of the/CC) porous heterostructure material comprises the following steps:
a）Ni(OH)2preparation of/CC: putting the pretreated carbon cloth into a furnace containing NiCl2·6H2O、NH4F. Reacting in an aqueous solution of urea at 80-150 ℃ for 6-10 h, cooling, taking out, washing with deionized water and ethanol, performing ultrasonic treatment, and performing vacuum drying at 50 ℃ for 2 h to obtain Ni (OH) grown on the surface of the carbon cloth2/CC, wherein the NiCl2·6H2The concentration of the O solution is 2-10 mmol/mL, NH4The concentration of the F solution is 2-10 mmol/mL, and the concentration of the urea solution is 10-20 mmol/mL;
b）NiS2preparation of CC precursor: reacting Ni (OH)2Calcining CC at 300-600 ℃ for 1-6 h, cooling to room temperature, taking out, putting into an ethanol solution containing thioacetamide, reacting for 4-10 h at 120-180 ℃, washing the cooled carbon cloth with water and ethanol respectively, carrying out moderate ultrasound, and carrying out vacuum drying at 50 ℃ for 2 h to obtain NiS growing on the surface of the carbon cloth2The concentration of the ethanol solution of the thioacetamide is 50-200 mg/mL;
c）Co-MoS2/NiS2preparation of/CC heterostructure: mixing NiS2CC adding thiourea and (NH)4)6Mo7O24·4H2O、Co(NO3)2·6H2Reacting in an O water solution at 180-240 ℃ for 10-24 h, washing the cooled carbon cloth with water and ethanol respectively, performing ultrasonic treatment, and performing vacuum drying at 50 ℃ for 2 h to obtain porous Co-MoS2/NiS2The material with a/CC heterostructure, wherein the concentration of the thiourea solution is 80-200 mg/mL (NH)4)6Mo7O24·4H2The concentration of the O solution is 50-200 mg/mL, and the concentration of Co (NO) is3)2·6H2The concentration of the O solution is 2-15 mg/mL.
In a preferred embodiment of the present invention, the size of the pretreated carbon cloth of step a) is about 2 × 2cm, 3M HNO3And (5) fully soaking.
In the preferred embodiment of the invention, the NiCl in the step a) is2·6H2The concentration of the O solution is 4 mmol/mL, NH4The concentration of the F solution is 8 mmol/mL, and the concentration of the urea solution is 15 mmol/mL; said Ni (OH)2The reaction temperature and reaction time for the growth of/CC are preferably 100 ℃ and 10 hours, respectively.
In the preferred embodiment of the present invention, the step b) is performed by adding Ni (OH)2the/CC is calcined at 350 ℃ for 2 h.
In the preferred embodiment of the invention, the concentration of the ethanol solution of the thioacetamide in the step b) is 4 mg/mL, and NiS2The reaction temperature and reaction time for the/CC growth are preferably 120 ℃ and 8 h, respectively.
In a preferred embodiment of the invention, the concentration of the thiourea solution in the step c) is 4 mg/mL (NH)4)6Mo7O24·4H2O solution concentration 2 mg/mL, Co (NO)3)2·6H2The concentration of the O solution is 0.3 mg/mL; the Co-MoS2/NiS2The reaction temperature/CC and the reaction time are preferably 200 ℃ and 24 h, respectively.
It is also an object of the present invention to prepare Co-MoS2/NiS2The overall appearance of the/CC composite material is nano sheets uniformly dispersed on carbon cloth fibers, the height of the nano sheets is about 1 mu m, and smaller MoS is distributed on the nano sheets2The microsphere assembled by the nano sheets has a 3D open pore passage and is applied to hydrogen evolution by water electrolysis.
Electrocatalytic hydrogen evolution performance test experiment
The three-electrode system is selected to measure the hydrogen evolution performance of the electrolyzed water with 0.5 mol/L H2SO4The solution is used as electrolyte, and the prepared Co-MoS is used2/NiS2the/CC catalyst is used as a working electrode, Ag/AgCl is used as a reference electrode, a platinum wire or a carbon rod is used as a counter electrode, and the LSV polarization curve is tested.
Advantages of the invention
(1) Selecting carbon cloth as a substrate, and preparing Co-MoS by a bottom-up method2/NiS2CC, simple and controllable operation process and high product load rate;
(2) prepared graded flaky Co-MoS2/NiS2/CC is from NiS2The nano-sheet is supported and grown in NiS2Co-doped MoS on nanosheets2Nanosheet, 2D NiS2The nano-sheet has high specific surface area and conductivity, can enhance the electron transmission efficiency, improve the dispersibility of the catalyst and accelerate the basic reaction of the water cracking step;
（3）MoS2/NiS2the heterostructure has a synergistic effect, so that the number of active sites is increased, and the existence of a heterogeneous interface adjusts the electron dispersibility, can promote the electron transfer and improve the chemical adsorption capacity of the catalyst. The 3D open type porous nanosheet formed by the heterostructure is beneficial to gas release;
(4) a small amount of Co is doped to further adjust the electronic structure of a catalytic interface and replace MoS2Part of Mo atoms in the middle layer of the sandwich structure. Because of the grain diameter difference of two metal atoms and Co doping, interface defects and sulfur vacancies are caused, which are beneficial to the adsorption of catalytic reaction intermediates, thereby improving the electrocatalytic performance.
Advantageous effects
The invention discloses a cobalt-doped porous heterostructure material growing from bottom to top and a preparation method thereof, wherein the material has the advantages of being porous, high in specific surface area, large in number of active centers, high in exposure ratio and the like, and shows good catalytic activity in an electrolytic water hydrogen evolution reaction. The method has the advantages of simple process, relatively mild conditions, high catalyst yield, low production cost and the like, and can be used for large-scale production.
Drawings
FIG. 1. Ni (OH) prepared in example 52SEM of/CC nanoplate;
FIG. 2 NiS prepared in example 52SEM of/CC nanoplate;
FIG. 3 Co-MoS prepared in example 52/NiS2SEM of/CC nanoplate;
FIG. 4 Co-MoS prepared in example 52/NiS2EDS of CC nanoplate;
FIG. 5 Co-MoS prepared in example 52/NiS2TEM of/CC nanoplate.
Detailed Description
The present invention will be described in detail below with reference to examples to enable those skilled in the art to better understand the present invention, but the present invention is not limited to the following examples.
Example 1
Cobalt-doped MoS2/NiS2（Co-MoS2/NiS2The preparation method of the/CC) porous heterostructure material comprises the following steps:
a）NiS2preparation of CC precursor: subjecting to 3M HNO3The pretreated carbon cloth (about 2X 2 cm in size) is placed in a container containing NiCl2·6H2O（2 mmol/mL）、NH4F (4 mmol/mL) and urea (12 mmol/mL) react in 40 mL aqueous solution at 80 ℃ for 8 h, the mixture is taken out after cooling, and is respectively washed by deionized water and ethanol, ultrasonically treated and dried in vacuum at 50 ℃ for 2 h to obtain Ni (OH) growing on the surface of the carbon cloth2and/CC. Then, calcining the carbon cloth at 350 ℃ for 2 h, cooling to room temperature, taking out, putting the carbon cloth into 25 mL ethanol solution containing thioacetamide (2 mg/mL), reacting at 120 ℃ for 6 h, washing the cooled carbon cloth with water and ethanol respectively, carrying out moderate ultrasound, and carrying out vacuum drying at 50 ℃ for 2 h to obtain NiS growing on the surface of the carbon cloth2/CC。
b）Co-MoS2/NiS2Preparation of/CC heterostructure: mixing NiS2CC is put into a reactor containing thiourea (2.5 mg/mL), (NH)4)6Mo7O24·4H2O（1.25 mg/mL）、Co(NO3)2·6H2Reacting O (0.05 mg/mL) in 40 mL aqueous solution at 200 ℃ for 12 h, washing the cooled carbon cloth with water and ethanol respectively, performing ultrasonic treatment, and performing vacuum drying at 50 ℃ for 2 h to obtain the porous Co-MoS2/NiS2a/CC heterostructure material.
When the current density reaches 10 mA/cm-2The overpotential required is 193 mV.
Example 2
Cobalt-doped MoS2/NiS2（Co-MoS2/NiS2The preparation method of the/CC) porous heterostructure material comprises the following steps:
a）NiS2preparation of CC precursor: subjecting to 3M HNO3The pretreated carbon cloth (about 2X 2 cm in size) is placed in a container containing NiCl2·6H2O（2 mmol/mL）、NH4F (2 mmol/mL) and urea (10 mmol/mL) react in 40 mL aqueous solution at 100 ℃ for 6 h, the mixture is taken out after cooling, and is respectively washed by deionized water and ethanol, ultrasonically treated and dried in vacuum at 50 ℃ for 2 h to obtain Ni (OH) growing on the surface of the carbon cloth2and/CC. Then, calcining the carbon cloth at 350 ℃ for 2 h, cooling to room temperature, taking out, putting the carbon cloth into 25 mL ethanol solution containing thioacetamide (6 mg/mL), reacting at 180 ℃ for 4 h, washing the cooled carbon cloth with water and ethanol respectively, carrying out moderate ultrasound, and carrying out vacuum drying at 50 ℃ for 2 h to obtain NiS growing on the surface of the carbon cloth2/CC。
b）Co-MoS2/NiS2Preparation of/CC heterostructure: mixing NiS2CC is put into a reaction kettle containing thiourea (2 mg/mL), (NH)4)6Mo7O24·4H2O（2 mg/mL）、Co(NO3)2·6H2Reacting O (0.15 mg/mL) in 40 mL aqueous solution at 180 ℃ for 10 h, washing the cooled carbon cloth with water and ethanol respectively, performing ultrasonic treatment, and performing vacuum drying at 50 ℃ for 2 h to obtain the porous Co-MoS2/NiS2a/CC heterostructure material.
When the current density reaches 10 mA/cm-2The overpotential required is 117 mV.
Example 3
Cobalt-doped MoS2/NiS2（Co-MoS2/NiS2The preparation method of the/CC) porous heterostructure material comprises the following steps:
a）NiS2preparation of CC precursor: subjecting to 3M HNO3The pretreated carbon cloth (about 2X 2 cm in size) is placed in a container containing NiCl2·6H2O（4 mmol/mL）、NH4F (6 mmol/mL) and urea (15 mmol/mL) react in 40 mL aqueous solution at 150 ℃ for 6 h, the mixture is taken out after cooling, and is respectively washed by deionized water and ethanol, ultrasonically treated and dried in vacuum at 50 ℃ for 2 h to obtain Ni (OH) growing on the surface of the carbon cloth2and/CC. Subsequently, it was calcined at 350 ℃Cooling to room temperature, taking out, adding into 25 mL ethanol solution containing thioacetamide (4 mg/mL), reacting at 150 deg.C for 6 h, washing cooled carbon cloth with water and ethanol respectively, performing moderate ultrasound treatment, and vacuum drying at 50 deg.C for 2 h to obtain NiS grown on the surface of carbon cloth2/CC。
b）Co-MoS2/NiS2Preparation of/CC heterostructure: mixing NiS2CC is put into a reactor containing thiourea (3 mg/mL), (NH)4)6Mo7O24·4H2O（2 mg/mL）、Co(NO3)2·6H2Reacting O (0.15 mg/mL) in 40 mL aqueous solution at 240 ℃ for 12 h, washing the cooled carbon cloth with water and ethanol respectively, performing ultrasonic treatment, and performing vacuum drying at 50 ℃ for 2 h to obtain the porous Co-MoS2/NiS2a/CC heterostructure material.
When the current density reaches 10 mA/cm-2The overpotential required is 135 mV.
Example 4
Cobalt-doped MoS2/NiS2（Co-MoS2/NiS2The preparation method of the/CC) porous heterostructure material comprises the following steps:
a）NiS2preparation of CC precursor: subjecting to 3M HNO3The pretreated carbon cloth (about 2X 2 cm in size) is placed in a container containing NiCl2·6H2O（6 mmol/mL）、NH4F (8 mmol/mL) and urea (18 mmol/mL) react in 40 mL aqueous solution at 120 ℃ for 10 h, the mixture is taken out after cooling, and is respectively washed by deionized water and ethanol, ultrasonically treated and dried in vacuum at 50 ℃ for 2 h to obtain Ni (OH) growing on the surface of the carbon cloth2and/CC. Then, calcining the carbon cloth at 350 ℃ for 2 h, cooling to room temperature, taking out, putting the carbon cloth into 25 mL ethanol solution containing thioacetamide (4.8 mg/mL), reacting at 120 ℃ for 8 h, washing the cooled carbon cloth with water and ethanol respectively, moderately performing ultrasonic treatment, and performing vacuum drying at 50 ℃ for 2 h to obtain NiS growing on the surface of the carbon cloth2/CC。
b）Co-MoS2/NiS2Preparation of/CC heterostructure: mixing NiS2PerCC is added with a solution containing thiourea (3.75 mg/mL), (NH)4)6Mo7O24·4H2O（2.5 mg/mL）、Co(NO3)2·6H2Reacting O (0.3 mg/mL) in 40 mL aqueous solution at 200 ℃ for 20 h, washing the cooled carbon cloth with water and ethanol respectively, performing ultrasonic treatment, and performing vacuum drying at 50 ℃ for 2 h to obtain the porous Co-MoS2/NiS2a/CC heterostructure material.
When the current density reaches 10 mA/cm-2The overpotential required is 207 mV.
Example 5
Cobalt-doped MoS2/NiS2（Co-MoS2/NiS2The preparation method of the/CC) porous heterostructure material comprises the following steps:
a）NiS2preparation of CC precursor: subjecting to 3M HNO3The pretreated carbon cloth (about 2X 2 cm in size) is placed in a container containing NiCl2·6H2O（4 mmol/mL）、NH4F (8 mmol/mL) and urea (15 mmol/mL) react in 40 mL aqueous solution at 100 ℃ for 10 h, the mixture is taken out after cooling, and is respectively washed by deionized water and ethanol, ultrasonically treated and dried in vacuum at 50 ℃ for 2 h to obtain Ni (OH) growing on the surface of the carbon cloth2and/CC. Then, calcining the carbon cloth at 350 ℃ for 2 h, cooling to room temperature, taking out, putting the carbon cloth into 25 mL ethanol solution containing thioacetamide (4 mg/mL), reacting at 120 ℃ for 8 h, washing the cooled carbon cloth with water and ethanol respectively, carrying out moderate ultrasound, and carrying out vacuum drying at 50 ℃ for 2 h to obtain NiS growing on the surface of the carbon cloth2/CC。
b）Co-MoS2/NiS2Preparation of/CC heterostructure: mixing NiS2/CC addition of thiourea (4 mg/mL), (NH)4)6Mo7O24·4H2O（2 mg/mL）、Co(NO3)2·6H2Reacting O (0.3 mg/mL) in 40 mL aqueous solution at 200 ℃ for 24 h, washing the cooled carbon cloth with water and ethanol respectively, performing ultrasonic treatment, and performing vacuum drying at 50 ℃ for 2 h to obtain the porous Co-MoS2/NiS2a/CC heterostructure material.
When the current density reaches 10 mA/cm-2The overpotential required is 82 mV.
Example 6
Cobalt-doped MoS2/NiS2（Co-MoS2/NiS2The preparation method of the/CC) porous heterostructure material comprises the following steps:
a）NiS2preparation of CC precursor: subjecting to 3M HNO3The pretreated carbon cloth (about 2X 2 cm in size) is placed in a container containing NiCl2·6H2O（10 mmol/mL）、NH4F (10 mmol/mL) and urea (20 mmol/mL) react in 40 mL aqueous solution at 120 ℃ for 8 h, the mixture is taken out after cooling, and is respectively washed by deionized water and ethanol, ultrasonically treated and dried in vacuum at 50 ℃ for 2 h to obtain Ni (OH) growing on the surface of the carbon cloth2and/CC. Then, calcining the carbon cloth at 350 ℃ for 2 h, cooling to room temperature, taking out, putting the carbon cloth into 25 mL ethanol solution containing thioacetamide (8 mg/mL), reacting at 180 ℃ for 10 h, washing the cooled carbon cloth with water and ethanol respectively, carrying out moderate ultrasound, and carrying out vacuum drying at 50 ℃ for 2 h to obtain NiS growing on the surface of the carbon cloth2/CC。
b）Co-MoS2/NiS2Preparation of/CC heterostructure: mixing NiS2CC is put into a reactor containing thiourea (5 mg/mL), (NH)4)6Mo7O24·4H2O（5 mg/mL）、Co(NO3)2·6H2Reacting O (0.4 mg/mL) in 40 mL aqueous solution at 240 ℃ for 24 h, washing the cooled carbon cloth with water and ethanol respectively, performing ultrasonic treatment, and performing vacuum drying at 50 ℃ for 2 h to obtain the porous Co-MoS2/NiS2a/CC heterostructure material.
When the current density reaches 10 mA/cm-2The overpotential required is 169 mV.
The above description is only an embodiment of the present invention, and not intended to limit the scope of the present invention, and all modifications of equivalent structures and equivalent processes performed by the present invention or directly or indirectly applied to other related technical fields are included in the scope of the present invention.
Claims (10)
1. Cobalt-doped MoS2/NiS2The preparation method of the porous heterostructure material is characterized by comprising the following steps：
a) Putting the pretreated carbon cloth into a furnace containing NiCl2·6H2O、NH4F. Reacting in an aqueous solution of urea at 80-150 ℃ for 6-10 h, cooling, taking out, washing with deionized water and ethanol, performing ultrasonic treatment, and performing vacuum drying at 50 ℃ for 2 h to obtain Ni (OH) grown on the surface of the carbon cloth2/CC, wherein the NiCl2·6H2The concentration of the O solution is 2-10 mmol/mL, NH4The concentration of the F solution is 2-10 mmol/mL, and the concentration of the urea solution is 10-20 mmol/mL;
b) reacting Ni (OH)2Calcining CC at 300-600 ℃ for 1-6 h, cooling to room temperature, taking out, putting into an ethanol solution containing thioacetamide, reacting for 4-10 h at 120-180 ℃, washing the cooled carbon cloth with water and ethanol respectively, carrying out moderate ultrasound, and carrying out vacuum drying at 50 ℃ for 2 h to obtain NiS growing on the surface of the carbon cloth2The concentration of the ethanol solution of the thioacetamide is 50-200 mg/mL;
c) mixing NiS2CC adding thiourea and (NH)4)6Mo7O24·4H2O、Co(NO3)2·6H2Reacting in an O water solution at 180-240 ℃ for 10-24 h, washing the cooled carbon cloth with water and ethanol respectively, performing ultrasonic treatment, and performing vacuum drying at 50 ℃ for 2 h to obtain porous Co-MoS2/NiS2The material is a/CC heterostructure material, wherein the concentration of the thiourea solution is 80-200 mg/mL; (NH)4)6Mo7O24·4H2The concentration of the O solution is 50-200 mg/mL, and the concentration of Co (NO) is3)2·6H2The concentration of the O solution is 2-15 mg/mL.
2. The cobalt-doped MoS of claim 12/NiS2The preparation method of the porous heterostructure material is characterized by comprising the following steps: the pretreated carbon cloth of the step a) has the size of about 2 multiplied by 2 cm and is subjected to 3M HNO3And (5) fully soaking.
3. The cobalt-doped MoS of claim 12/NiS2The preparation method of the porous heterostructure material is characterized by comprising the following steps: step a) said NiCl2·6H2The concentration of the O solution is 4 mmol/mL, NH4The concentration of the F solution is 8 mmol/mL, and the concentration of the urea solution is 15 mmol/mL.
4. The cobalt-doped MoS of claim 12/NiS2The preparation method of the porous heterostructure material is characterized by comprising the following steps: step a) said Ni (OH)2The CC growth reaction temperature is 100 ℃ and the time is 10 h.
5. The cobalt-doped MoS of claim 12/NiS2The preparation method of the porous heterostructure material is characterized by comprising the following steps: step b) said reaction of Ni (OH)2the/CC is calcined at 350 ℃ for 2 h.
6. The cobalt-doped MoS of claim 12/NiS2The preparation method of the porous heterostructure material is characterized by comprising the following steps: the ethanol solution of thioacetamide in the step b) has the concentration of 4 mg/mL, and NiS2The reaction temperature of CC growth is 120 ℃ and the time is 8 h.
7. The cobalt-doped MoS of claim 12/NiS2The preparation method of the porous heterostructure material is characterized by comprising the following steps: the concentration of the thiourea solution in the step c) is 4 mg/mL, (NH)4)6Mo7O24·4H2O solution concentration 2 mg/mL, Co (NO)3)2·6H2The concentration of the O solution is 0.3 mg/mL; the Co-MoS2/NiS2Reaction time of 24 h at CC reaction temperature of 200 ℃.
8. Cobalt-doped MoS prepared according to any of the methods of claims 1-72/NiS2A porous heterostructure material.
9. The cobalt-doped MoS of claim 82/NiS2Porous heterostructure material, characterized in that: the overall appearance of the carbon cloth is nano sheets uniformly dispersed on carbon cloth fibers, the height of the nano sheets is about 1 mu m, and the nano sheets are distributed smallerMoS2The microsphere assembled by the nano sheets has a 3D open pore channel.
10. Use of a material according to claim 8 or 9, wherein: it is applied to electrolyzing water to generate hydrogen.
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Cited By (4)
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| CN113789545A (en) * | 2021-09-26 | 2021-12-14 | 中汽创智科技有限公司 | Water electrolysis catalyst and preparation method and application thereof |
| CN114318407A (en) * | 2021-12-03 | 2022-04-12 | 华南理工大学 | 1T-MoS for electrocatalytic hydrogen evolution2Catalyst with NiS heterogeneous interface structure and preparation method and application thereof |
| NL2030850A (en) * | 2021-12-09 | 2022-05-24 | Univ Guilin Technology | Flexible composite electrode material as well as preparation method and use thereof |
| CN115821305A (en) * | 2023-02-14 | 2023-03-21 | 北京理工大学 | Electrocatalyst and preparation method and application thereof |
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