阅读说明：本技术 催化制氢材料的制备方法、催化制氢材料及应用 (Preparation method of catalytic hydrogen production material, catalytic hydrogen production material and application ) 是由 李华 陈莹 金婷 刘守清 于 2021-10-11 设计创作，主要内容包括：本发明公开了催化制氢材料的制备方法、催化制氢材料及应用,其中制备方法包括A、制备2H-MoS-(2)基体；B、将2H-MoS-(2)基体置于含杂单原子盐的溶液中,采用热交换反应将杂单原子以单原子形态均匀地分散于2H-MoS-(2)基体表面,杂单原子为锰原子、铁原子中任一。本发明获得的电催化制氢材料,其单原子既具有高分散性,又具有高稳定性,其整体同时又具有高的析氢活性,为替代贵金属Pt催化剂提供了价格低廉的技术方案。(The invention discloses a preparation method of a catalytic hydrogen production material, the catalytic hydrogen production material and application thereof, wherein the preparation method comprises the steps of A, 2H-MoS preparation 2 A substrate; B. 2H-MoS 2 The substrate is placed in a solution containing a salt of a heteromonogen, and the heteromonogen is uniformly dispersed in the form of a monoatomic atom in 2H-MoS by a heat exchange reaction 2 The surface of the substrate is provided with any one of manganese atoms and iron atoms. The obtained electrocatalytic hydrogen production material has the advantages that the monoatomic group has high dispersibility and high stability, the whole body has high hydrogen evolution activity, and a technical scheme with low price is provided for replacing a noble metal Pt catalyst.)

1. A method for preparing a catalytic hydrogen production material, which is characterized by comprising the following steps:

A. preparation of 2H-MoS₂A substrate;

B. 2H-MoS₂The substrate is placed in a solution containing a salt of a heteromonogen, and the heteromonogen is uniformly dispersed in the form of a monoatomic atom in 2H-MoS by a heat exchange reaction₂And on the surface of the substrate, the hetero-monoatomic atoms are any one of manganese atoms and iron atoms.

2. The method for preparing the catalytic hydrogen production material according to claim 1, wherein the step A is a hydrothermal method for preparing 2H-MoS in a high-pressure reaction kettle₂A substrate.

3. The method of producing a catalytic hydrogen production material according to claim 2, wherein step a is: preparing a sulfur source water solution and a molybdate water solution; slowly dripping the sulfur source water solution into the molybdate water solution under the stirring condition, and uniformly mixing; transferring the mixed solution into a hydrothermal high-pressure reaction kettle, reacting at the temperature of 200 ℃ and 250 ℃ for 20-30h, and cooling to room temperature; separating and removing impurities to obtain 2H-MoS₂A substrate.

4. The method of producing a catalytic hydrogen production material according to claim 1, wherein step B is: preparing a solution containing a salt of a heteromonogen; 2H-MoS is stirred₂Dispersing the matrix in a solution containing a salt of a heteromonogen; transferring the mixed solution into a hydrothermal high-pressure reaction kettle, reacting in a blast oven at the temperature of 200-250 ℃ for 8-12h, and cooling to room temperature; separating and removing impurities to obtain the catalytic hydrogen production material.

5. The method of producing a catalytic hydrogen production material according to claim 1 or 4, wherein the salt containing a heteromonogen is a hydrochloride, a sulfate, or a nitrate.

6. The method of claim 1, wherein the heteromonoatom is in the range of 2H-MoS₂The loading on the substrate is not more than 4.5 mole percent based on the total number of atoms.

7. A method for producing a material for catalytic hydrogen production according to claim 3, wherein the sulfur source is thiourea or sodium thiosulfate.

8. A method for producing a material for catalytic hydrogen production according to claim 3, wherein the molybdate is sodium molybdate or potassium molybdate.

9. A catalytic hydrogen production material produced by the method for producing a catalytic hydrogen production material according to claim 8.

10. Use of a catalytic hydrogen production material according to claim 9 for catalytic hydrogen production.

Technical Field

The invention relates to a new energy technology, in particular to a preparation method of a catalytic hydrogen production material, the catalytic hydrogen production material and application.

Background

Hydrogen energy is considered as a very end-use alternative to fossil energy and is one of the best ways to achieve carbon peaking and carbon neutralization. Hydrogen is used as a carrier of energy, and its main sources are "grey hydrogen", "blue hydrogen" and "green hydrogen" routes. Power generation by photovoltaicThe wind power generation and the hydroelectric generation are used for producing hydrogen by electrolyzing water, so that carbon peak reaching and carbon neutralization can be fundamentally realized. However, the noble metal platinum electrode used for hydrogen production by electrolysis of water is limited because it is expensive. For this reason, non-noble metal hydrogen evolution electrocatalysts have been developed. Molybdenum sulfide (MoS)₂) This is of particular interest because the sulfur edge in its structure adsorbs hydrogen similarly to Pt metal. It has three structures, namely 1T-MoS₂、2H-MoS₂And 3R-MoS₂。1T-MoS₂The octahedron coordination of the structure has metal property and belongs to a metastable state structure; 2H-MoS₂The crystal form contains two Mo-S units and belongs to a stable state structure; 3R-MoS₂Crystal form ratio of 2H-MoS₂The crystal form has one more Mo-S unit, namely contains three Mo-S units and also belongs to a metastable state structure. 1T-MoS₂And 3R-MoS₂The stability is not high, and the catalyst is not an ideal hydrogen evolution electrocatalyst; 2H-MoS₂It is relatively stable, but its conductivity is poor. Due to pure 2H-MoS₂The hydrogen evolution electrocatalytic activity is not high, so that the molybdenum sulfide composite electrocatalyst is prepared by compounding the molybdenum sulfide composite electrocatalyst with graphene, carbon nano tubes and other materials so as to improve the electrocatalytic performance of the molybdenum sulfide composite electrocatalyst. In addition, people hope to improve the electrocatalytic performance by the doping mode of metal ions. Nevertheless, the atom utilization of these electrocatalysts is not high.

The information disclosed in this background section is only for enhancement of understanding of the general background of the invention and should not be taken as an acknowledgement or any form of suggestion that this information forms the prior art already known to a person skilled in the art.

Disclosure of Invention

The invention aims to provide a catalytic hydrogen production material, a preparation method and application, which can obtain the catalytic hydrogen production material with low toxicity, low pollution and high efficiency by improving the distribution form of specific heteromonoatoms on a specific substrate material, and has the advantages of simple and easy preparation, environmental protection and the like.

To achieve the above object, an embodiment of the present invention provides a method for preparing a catalytic hydrogen production material, including: A. preparation of 2H-MoS₂A substrate; B. 2H-MoS₂The substrate is placed in a solution containing a salt of a heteromonogen, and the heteromonogen is uniformly dispersed in the form of a monoatomic atom in 2H-MoS by a heat exchange reaction₂The surface of the substrate is provided with any one of manganese atoms and iron atoms. The invention effectively overcomes the contradiction between high dispersion and stability of the monatomic form in the interface distribution by adopting a specific preparation scheme, namely the contradiction that the high dispersion is not easy to stabilize and the high dispersion is difficult to realize, thereby obtaining a stable monatomic catalytic structure without complexing, vacancy and the like.

In one or more embodiments of the invention, step A is hydrothermal preparation of 2H-MoS in an autoclave₂A substrate.

In one or more embodiments of the invention, step a is: preparing a sulfur source water solution and a molybdate water solution; slowly dripping the sulfur source water solution into the molybdate water solution under the stirring condition, and uniformly mixing; transferring the mixed solution into a hydrothermal high-pressure reaction kettle, reacting at the temperature of 200 ℃ and 250 ℃ for 20-30h, and cooling to room temperature; separating and removing impurities to obtain 2H-MoS₂A substrate. The sulfur source preferably includes, but is not limited to, thiourea, sodium thiosulfate, and the like, and in practice may be a single solute solution or a multi-solute solution. The molybdate preferably includes, but is not limited to, sodium molybdate, potassium molybdate, and the like, and may be a single solute solution or a multi-solute solution in practice.

In one or more embodiments of the invention, step B is: preparing a solution containing a salt of a heteromonogen; 2H-MoS is stirred₂Dispersing the matrix in a solution containing a salt of a heteromonogen; transferring the mixed solution into a hydrothermal high-pressure reaction kettle, reacting in a blast oven at the temperature of 200-250 ℃ for 8-12h, and cooling to room temperature; separating and removing impurities to obtain the catalytic hydrogen production material.

In one or more embodiments of the invention, the loading of the heteromonogen on the substrate is not greater than 4.5 mole percent based on the total number of atoms.

In one or more embodiments of the present invention, the salt containing heteromonogen includes, but is not limited to, hydrochloride, sulfate, nitrate, etc., and may be a single solute solution or a multi-solute solution in practice.

In one or more embodiments of the present invention, the catalytic hydrogen production material is produced by a method of producing a catalytic hydrogen production material as described above.

In one or more embodiments of the invention, a catalytic hydrogen production material as described above is used in catalytic hydrogen production.

In the scheme, the reaction pressure in the high-pressure reaction kettle is 5-35 bar.

In one or more embodiments of the invention, a catalytic hydrogen production material is used in catalytic hydrogen production.

Compared with the prior art, the catalytic hydrogen production material provided by the embodiment of the invention has the characteristics of high atom utilization rate and high electrocatalytic hydrogen evolution activity, and can obviously improve the capacity of preparing hydrogen by electrocatalysis. The hydrogen prepared by the invention is high-purity hydrogen, does not contain carbon monoxide, hydrogen sulfide and other pollutants which poison fuel cell electrode materials, and the preparation method of the manganese monatomic/molybdenum sulfide electrocatalytic material is simple and easy to implement, and is green and environment-friendly. Meanwhile, the catalytic hydrogen production material disclosed by the invention has high-dispersion monoatomic property, high stability and high hydrogen evolution activity, and provides a low-cost alternative scheme for replacing a noble metal Pt catalyst.

Drawings

FIG. 1 is a powder diffraction pattern of a manganese monatomic/molybdenum sulfide material according to an embodiment of the present invention;

FIG. 2 is a microscopic image of a manganese monatomic/molybdenum sulfide material according to an embodiment of the present invention, wherein (a), Mn-MoS₂Spherical aberration electron micrographs of the samples; (b) Mn-MoS₂A spherical aberration electron microscope element mapping chart of the sample; (c) mo element distribution diagram; (d) distribution diagram of S element; (e) the distribution diagram of Mn element; (f) is Mn-MoS₂High resolution electron microscopy images of; (g) f, is an enlarged view of a single manganese atom in a selected area of a dotted line frame;

FIG. 3 is a linear scanning hydrogen evolution curve according to an embodiment of the present invention, wherein (a) pure MoS₂(b) in the range of 1.0mol/LMn²⁺Mn-MoS prepared in solution₂And (c) is at 1.5mol/LMn²⁺Mn-MoS prepared in solution₂(d) at 2.0mol/LMn²⁺Mn-MoS prepared in solution₂(e) at 2.5mol/LMn²⁺Mn-MoS prepared in solution₂(f) Pt/C (10%) and (g) graphite powder GP;

FIG. 4 is a powder diffraction pattern according to an embodiment of the present invention, wherein (a)2H-MoS₂The powder diffraction curve of (1); (b) powder diffraction profile of iron monatomic-molybdenum sulfide;

FIG. 5 is a Fe-MoS according to an embodiment of the present invention₂Micrographs of samples wherein (a)₂Spherical aberration electron micrographs of the samples; Fe-MoS₂A spherical aberration electron microscope element mapping chart of the sample; (c) a distribution diagram of Mo element; (d) distribution diagram of S element; (e) is a distribution diagram of Fe element; (f) is Fe-MoS₂High resolution electron microscopy images of; (g) f is an enlarged view of the iron monoatomic region outlined by the dotted line;

FIG. 6 is a linear scan hydrogen evolution curve according to an embodiment of the present invention: (a) pure MoS₂(b) at 1.0mol/LFe^{2 +}Fe-MoS prepared in solution₂(c) at 1.5mol/LFe²⁺Fe-MoS prepared in solution₂(d) at 2.0mol/LFe²⁺Fe-MoS prepared in solution₂(e) at 2.5mol/LFe²⁺Fe-MoS prepared in solution₂(f) Pt/C (10%) and (g) graphite powder.

Detailed Description

The following detailed description of the present invention is provided in conjunction with the accompanying drawings, but it should be understood that the scope of the present invention is not limited to the specific embodiments.

Throughout the specification and claims, unless explicitly stated otherwise, the word "comprise", or variations such as "comprises" or "comprising", will be understood to imply the inclusion of a stated element or component but not the exclusion of any other element or component.

Example 11

The method comprises the following steps: MoS preparation by hydrothermal method₂. 0.010mol of sodium molybdate (Na)₂MoO₄·2H₂O) is dissolved in 30.0mL deionized water and ultrasonically dispersed for 30 minutesA clock. Followed by 0.040mol of thiourea [ (NH)₂)₂CS]Dissolved in 30.0mL of deionized water and ultrasonically dispersed for 30 minutes as well. The thiourea aqueous solution is slowly dripped into the sodium molybdate aqueous solution under magnetic stirring, and is stirred for 1 hour to be uniformly mixed. Then the mixed solution is moved into a 100mL hydrothermal high-pressure reaction kettle and placed in a blast oven at 200 ℃ for reaction for 24 hours. After the reaction is completed, cooling to room temperature, carrying out vacuum filtration, washing with deionized water and ethanol to be neutral, and removing soluble substances. Finally, drying the finally obtained product in a vacuum drying oven at 60 ℃ for 6h to obtain MoS₂And (3) sampling.

Step two: manganese monatomic self-assembly molybdenum disulfide is prepared by a thermal equilibrium method. 6.0g of MnCl₂·4H₂O was dissolved in 30.0mL of deionized water to give a 1.0mol/L solution. Then, 0.4g of MoS was magnetically stirred₂Dispersed in MnCl₂The solution was kept for 1 hour. The mixed solution is transferred into a 50mL hydrothermal high-pressure reaction kettle and placed in a blast oven at 200 ℃ for reaction for 8 hours. After the reaction is completed, cooling to room temperature, carrying out vacuum filtration, washing with deionized water and ethanol to be neutral, and removing soluble substances. Drying the finally obtained product in a vacuum drying oven at 60 ℃ for 6h to obtain Mn1.0-MoS₂The sample, i.e. the sample obtained in a manganese salt solution with a concentration of 1M, is as follows.

The research adopts a three-electrode system to carry out an electrocatalytic hydrogen evolution experiment on a sample. The working electrode was prepared as follows: weighing 0.10g of sample to be detected and 0.15g of graphite powder, grinding the sample to be detected and the graphite powder by using an agate mortar to obtain a fully mixed powder sample, dripping 0.1ml of silicone oil into the fully mixed powder sample, and fully stirring to obtain a paste sample with fine and uniform particles. The sample was filled into a carbon paste electrode and polished. The Pt sheet electrode was used as a counter electrode, the saturated calomel electrode was used as a reference electrode, and the electrolyte solution was KOH at a concentration of 1.0M. A linear scan test was carried out at normal temperature and pressure, and a hydrogen evolution curve was obtained at a scan rate of 10mV/s as shown in curve (b) of FIG. 3.

Example 12

The method comprises the following steps: MoS preparation by hydrothermal method₂. 0.010mol of sodium molybdate (Na)₂MoO₄·2H₂O) is dissolved in30.0mL deionized water, and ultrasonically dispersed for 30 minutes. Followed by 0.040mol of thiourea [ (NH)₂)₂CS]Dissolved in 30.0mL of deionized water and ultrasonically dispersed for 30 minutes as well. The thiourea aqueous solution is slowly dripped into the sodium molybdate aqueous solution under magnetic stirring, and is stirred for 1 hour to be uniformly mixed. Then the mixed solution is moved into a 100mL hydrothermal high-pressure reaction kettle and placed in a blast oven at 200 ℃ for reaction for 24 hours. After the reaction is completed, cooling to room temperature, carrying out vacuum filtration, washing with deionized water and ethanol to be neutral, and removing soluble substances. Finally, drying the finally obtained product in a vacuum drying oven at 60 ℃ for 6h to obtain MoS₂And (3) sampling.

Step two: manganese monatomic self-assembly molybdenum disulfide is prepared by a thermal equilibrium method. 9.0g of MnCl₂·4H₂O was dissolved in 30.0mL of deionized water to give a 1.5mol/L solution. Then, 0.4g of MoS was stirred magnetically₂Dispersed in MnCl₂The solution was kept for 1 hour. The mixed solution is transferred into a 50mL hydrothermal high-pressure reaction kettle and placed in a blast oven at 200 ℃ for reaction for 8 hours. After the reaction is completed, cooling to room temperature, carrying out vacuum filtration, washing with deionized water and ethanol to be neutral, and removing soluble substances. Drying the finally obtained product in a vacuum drying oven at 60 ℃ for 6h to obtain Mn1.5-MoS₂And (3) sampling.

The research adopts a three-electrode system to carry out an electrocatalytic hydrogen evolution experiment on a sample. The working electrode was prepared as follows: weighing 0.10g of sample to be detected and 0.15g of graphite powder, grinding the sample to be detected and the graphite powder by using an agate mortar to obtain a fully mixed powder sample, dripping 0.1ml of silicone oil into the fully mixed powder sample, and fully stirring to obtain a paste sample with fine and uniform particles. The sample was filled into a carbon paste electrode and polished. The Pt sheet electrode was used as a counter electrode, the saturated calomel electrode was used as a reference electrode, and the electrolyte solution was KOH at a concentration of 1.0M. A linear scan test was carried out at normal temperature and pressure, and a hydrogen evolution curve was obtained at a scan rate of 10mV/s as shown in curve (c) of FIG. 3.

Example 13

The method comprises the following steps: MoS preparation by hydrothermal method₂. 0.010mol of sodium molybdate (Na)₂MoO₄·2H₂O) dissolved in 30.0mL of deionized waterIn water and dispersed ultrasonically for 30 minutes. Followed by 0.040mol of thiourea [ (NH)₂)₂CS]Dissolved in 30.0mL of deionized water and ultrasonically dispersed for 30 minutes as well. The thiourea aqueous solution is slowly dripped into the sodium molybdate aqueous solution under magnetic stirring, and is stirred for 1 hour to be uniformly mixed. Then the mixed solution is moved into a 100mL hydrothermal high-pressure reaction kettle and placed in a blast oven at 200 ℃ for reaction for 24 hours. After the reaction is completed, cooling to room temperature, carrying out vacuum filtration, washing with deionized water and ethanol to be neutral, and removing soluble substances. Finally, drying the finally obtained product in a vacuum drying oven at 60 ℃ for 6h to obtain MoS₂And (3) sampling.

Step two: manganese monatomic self-assembly molybdenum disulfide is prepared by a thermal equilibrium method. 12.0g of MnCl₂·4H₂O was dissolved in 30.0mL of deionized water to give a 2.0mol/L solution. Then, 0.4g of MoS was stirred magnetically₂Dispersed in MnCl₂The solution was kept for 1 hour. The mixed solution is transferred into a 50mL hydrothermal high-pressure reaction kettle and placed in a blast oven at 200 ℃ for reaction for 8 hours. After the reaction is completed, cooling to room temperature, carrying out vacuum filtration, washing with deionized water and ethanol to be neutral, and removing soluble substances. Drying the finally obtained product in a vacuum drying oven at 60 ℃ for 6h to obtain Mn2.0-MoS₂And (3) sampling.

The research adopts a three-electrode system to carry out an electrocatalytic hydrogen evolution experiment on a sample. The working electrode was prepared as follows: weighing 0.10g of sample to be detected and 0.15g of graphite powder, grinding the sample to be detected and the graphite powder by using an agate mortar to obtain a fully mixed powder sample, dripping 0.1ml of silicone oil into the fully mixed powder sample, and fully stirring to obtain a paste sample with fine and uniform particles. The sample was filled into a carbon paste electrode and polished. The Pt sheet electrode was used as a counter electrode, the saturated calomel electrode was used as a reference electrode, and the electrolyte solution was KOH at a concentration of 1.0M. The linear scan test was performed at normal temperature and pressure, and the hydrogen evolution curve obtained at a scan rate of 10mV/s was shown in FIG. 3, curve (d), showing the best hydrogen evolution performance.

FIGS. 2(a) -2(g) show the dispersion state of manganese monoatomic atoms in the catalytic material, which indicates that the catalytic material obtained by the present embodiment has a high degree of dispersion of manganese monoatomic atoms, and is highly dispersed as a whole and substantially distributed in a monoatomic state.

Example 14

The method comprises the following steps: MoS preparation by hydrothermal method₂. 0.010mol of potassium molybdate (Na)₂MoO₄·2H₂O) was dissolved in 30.0mL of deionized water and ultrasonically dispersed for 30 minutes. 0.040mol of sodium thiosulfate was then dissolved in 30.0mL of deionized water and likewise dispersed ultrasonically for 30 minutes. The thiourea aqueous solution is slowly dripped into the sodium molybdate aqueous solution under magnetic stirring, and is stirred for 1 hour to be uniformly mixed. Then the mixed solution is moved into a 100mL hydrothermal high-pressure reaction kettle and placed in a blowing oven at 250 ℃ for reaction for 30 hours. After the reaction is completed, cooling to room temperature, carrying out vacuum filtration, washing with deionized water and ethanol to be neutral, and removing soluble substances. Finally, drying the finally obtained product in a vacuum drying oven at 60 ℃ for 6h to obtain MoS₂And (3) sampling.

Step two: manganese monatomic self-assembly molybdenum disulfide is prepared by a thermal equilibrium method. 18.83g of Mn (NO)₃)₂·4H₂O was dissolved in 30.0mL of deionized water to give a 2.5mol/L solution. Then, 0.4g of MoS was stirred magnetically₂Dispersed in MnCl₂The solution was kept for 1 hour. The mixed solution is transferred into a 50mL hydrothermal high-pressure reaction kettle and placed in a 250 ℃ air-blast oven for reaction for 12 hours. After the reaction is completed, cooling to room temperature, carrying out vacuum filtration, washing with deionized water and ethanol to be neutral, and removing soluble substances. Drying the finally obtained product in a vacuum drying oven at 60 ℃ for 6h to obtain Mn2.5-MoS₂And (3) sampling.

The research adopts a three-electrode system to carry out an electrocatalytic hydrogen evolution experiment on a sample. The working electrode was prepared as follows: weighing 0.10g of sample to be detected and 0.15g of graphite powder, grinding the sample to be detected and the graphite powder by using an agate mortar to obtain a fully mixed powder sample, dripping 0.1ml of silicone oil into the fully mixed powder sample, and fully stirring to obtain a paste sample with fine and uniform particles. The sample was filled into a carbon paste electrode and polished. The Pt sheet electrode was used as a counter electrode, the saturated calomel electrode was used as a reference electrode, and the electrolyte solution was KOH at a concentration of 1.0M. A linear scan test was carried out at normal temperature and pressure, and a hydrogen evolution curve was obtained at a scan rate of 10mV/s as shown in curve (e) of FIG. 3.

The electrochemical hydrogen evolution activity test in the embodiment of the invention comprises the following steps:

the working electrode was prepared as follows: weighing 0.10g of sample to be detected and 0.15g of graphite powder, grinding the sample to be detected and the graphite powder by using an agate mortar to obtain a fully mixed powder sample, dripping 0.1ml of silicone oil into the fully mixed powder sample, and fully stirring to obtain a paste sample with fine and uniform particles. The sample was filled into a carbon paste electrode and polished. The Pt sheet electrode was used as a counter electrode, the saturated calomel electrode was used as a reference electrode, and the electrolyte solution was KOH at a concentration of 1.0M. The LSV linear scan test was performed at room temperature and pressure, with a scan rate of 10 mV/s.

As shown in fig. 3. Mn-MoS synthesized under optimum production conditions at a Mn (II) concentration of 2.0mol/L₂The electrode, with an overpotential of 165mV, close to the Pt/C electrode, is much less than 462mV pure MoS₂Overpotential of the electrode; the Tafel slope is 58mV/Dec, and the excellent hydrogen evolution electrocatalytic activity is shown.

The powder diffraction pattern of the manganese monatomic/molybdenum sulfide material is shown in fig. 1, indicating the presence of molybdenum sulfide and manganese in the material. Diffraction peaks of the diffraction curve (a) of molybdenum sulfide at 2 θ of 12.55 °, 33.36 °, 39.42 °, 57.28 ° and 70.14 ° correspond to MoS₂(002) Diffraction crystal planes of (101), (103), (110) and (108). The diffraction peaks of the curve (b) at 2 θ of 14.01 °, 33.36 °, 39.42 °, 58.75 ° and 70.14 ° correspond to Mn — MoS₂(002) Diffraction crystal planes of (101), (103), (110) and (108).

Example 21

The method comprises the following steps: MoS preparation by hydrothermal method₂. 0.010mol of sodium molybdate (Na)₂MoO₄·2H₂O) was dissolved in 30.0mL of deionized water and ultrasonically dispersed for 30 minutes. Followed by 0.040mol of thiourea [ (NH)₂)₂CS]Dissolved in 30.0mL of deionized water and ultrasonically dispersed for 30 minutes as well. The thiourea aqueous solution is slowly dripped into the sodium molybdate aqueous solution under magnetic stirring, and is stirred for 1 hour to be uniformly mixed. Then the mixed solution is moved into a 100mL hydrothermal high-pressure reaction kettle and placed in a blast oven at 200 ℃ for reaction for 24 hours. After the reaction is completed, coolingCooling to room temperature, vacuum filtering, washing with deionized water and ethanol to neutrality, and removing soluble matter. Finally, drying the finally obtained product in a vacuum drying oven at 60 ℃ for 6h to obtain MoS₂And (3) sampling.

Step two: the monatomic iron assembled molybdenum disulfide is synthesized by a thermal equilibrium method. 6.09g of FeCl₂·4H₂O was dissolved in 30.0mL of deionized water to give a 1.0mol/L solution. Then, 0.4g of MoS was stirred magnetically₂Dispersed in FeCl₂The solution was kept for 1 hour. The mixed solution is transferred into a 50mL hydrothermal high-pressure reaction kettle and placed in a blast oven at 200 ℃ for reaction for 8 hours. After the reaction is completed, cooling to room temperature, carrying out vacuum filtration, washing with deionized water and ethanol to be neutral, and removing soluble substances. Drying the finally obtained product in a vacuum drying oven at 60 ℃ for 6h to obtain Fe1.0-MoS₂The sample obtained in the iron salt solution having a concentration of 1.0mol/L was the same as below.

Step three: electrocatalytic hydrogen evolution. The working electrode was prepared as follows: weighing 0.10g of sample to be detected and 0.15g of graphite powder, grinding the sample to be detected and the graphite powder by using an agate mortar to obtain a fully mixed powder sample, dripping 0.1ml of silicone oil into the fully mixed powder sample, and fully stirring to obtain a paste sample with fine and uniform particles. The sample was filled into a carbon paste electrode and polished. The Pt sheet electrode was used as a counter electrode, the saturated calomel electrode was used as a reference electrode, and the electrolyte solution was KOH at a concentration of 1.0M. A linear scan test was carried out at normal temperature and pressure, and a hydrogen evolution curve was obtained at a scan rate of 10mV/s as shown in curve (b) of FIG. 6.

Example 22

The method comprises the following steps: MoS preparation by hydrothermal method₂. 0.010mol of sodium molybdate (Na)₂MoO₄·2H₂O) was dissolved in 30.0mL of deionized water and ultrasonically dispersed for 30 minutes. Followed by 0.040mol of thiourea [ (NH)₂)₂CS]Dissolved in 30.0mL of deionized water and ultrasonically dispersed for 30 minutes as well. The thiourea aqueous solution is slowly dripped into the sodium molybdate aqueous solution under magnetic stirring, and is stirred for 1 hour to be uniformly mixed. Then the mixed solution is moved into a 100mL hydrothermal high-pressure reaction kettle and placed in a blast oven at 200 ℃ for reaction for 24 hours. After the reaction is finishedCooling to room temperature after completion, vacuum filtering, washing with deionized water and ethanol to neutrality, and removing soluble substances. Finally, drying the finally obtained product in a vacuum drying oven at 60 ℃ for 6h to obtain MoS₂And (3) sampling.

Step two: the thermal equilibrium method is adopted to prepare the iron monatomic self-assembled molybdenum disulfide. 9.14g of FeCl₂·4H₂O was dissolved in 30.0mL of deionized water to give a 1.5mol/L solution. Then, 0.4g of MoS was stirred magnetically₂Dispersed in FeCl₂The solution was kept for 1 hour. The mixed solution is transferred into a 50mL hydrothermal high-pressure reaction kettle and placed in a blast oven at 200 ℃ for reaction for 8 hours. After the reaction is completed, cooling to room temperature, carrying out vacuum filtration, washing with deionized water and ethanol to be neutral, and removing soluble substances. Drying the finally obtained product in a vacuum drying oven at 60 ℃ for 6h to obtain Fe1.5-MoS₂And (3) sampling.

The research adopts a three-electrode system to carry out an electrocatalytic hydrogen evolution experiment on a sample. The working electrode was prepared as follows: weighing 0.10g of sample to be detected and 0.15g of graphite powder, grinding the sample to be detected and the graphite powder by using an agate mortar to obtain a fully mixed powder sample, dripping 0.1ml of silicone oil into the fully mixed powder sample, and fully stirring to obtain a paste sample with fine and uniform particles. The sample was filled into a carbon paste electrode and polished. The Pt sheet electrode was used as a counter electrode, the saturated calomel electrode was used as a reference electrode, and the electrolyte solution was KOH at a concentration of 1.0M. The linear scan test was performed at normal temperature and pressure, and the hydrogen evolution curve obtained at a scan rate of 10mV/s was shown in FIG. 6, curve (c), which shows the best hydrogen evolution performance.

Example 23

The method comprises the following steps: MoS preparation by hydrothermal method₂. 0.010mol of sodium molybdate (Na)₂MoO₄·2H₂O) was dissolved in 30.0mL of deionized water and ultrasonically dispersed for 30 minutes. Followed by 0.040mol of thiourea [ (NH)₂)₂CS]Dissolved in 30.0mL of deionized water and ultrasonically dispersed for 30 minutes as well. The thiourea aqueous solution is slowly dripped into the sodium molybdate aqueous solution under magnetic stirring, and is stirred for 1 hour to be uniformly mixed. Then the mixed solution is moved into a 100mL hydrothermal high-pressure reaction kettle and is placed in a blast oven at 200 DEG CAnd reacting for 24 hours. After the reaction is completed, cooling to room temperature, carrying out vacuum filtration, washing with deionized water and ethanol to be neutral, and removing soluble substances. Finally, drying the finally obtained product in a vacuum drying oven at 60 ℃ for 6h to obtain MoS₂And (3) sampling.

Step two: the thermal equilibrium method is adopted to prepare the iron monatomic self-assembled molybdenum disulfide. 12.18g of FeCl₂·4H₂O was dissolved in 30.0mL of deionized water to give a 2.0mol/L solution. Then, 0.4g of MoS was stirred magnetically₂Dispersed in FeCl₂The solution was kept for 1 hour. The mixed solution is transferred into a 50mL hydrothermal high-pressure reaction kettle and placed in a blast oven at 200 ℃ for reaction for 8 hours. After the reaction is completed, cooling to room temperature, carrying out vacuum filtration, washing with deionized water and ethanol to be neutral, and removing soluble substances. Drying the finally obtained product in a vacuum drying oven at 60 ℃ for 6h to obtain Fe2.0-MoS₂And (3) sampling.

The research adopts a three-electrode system to carry out an electrocatalytic hydrogen evolution experiment on a sample. The working electrode was prepared as follows: weighing 0.10g of sample to be detected and 0.15g of graphite powder, grinding the sample to be detected and the graphite powder by using an agate mortar to obtain a fully mixed powder sample, dripping 0.1ml of silicone oil into the fully mixed powder sample, and fully stirring to obtain a paste sample with fine and uniform particles. The sample was filled into a carbon paste electrode and polished. The Pt sheet electrode was used as a counter electrode, the saturated calomel electrode was used as a reference electrode, and the electrolyte solution was KOH at a concentration of 1.0M. A linear scan test was carried out at normal temperature and pressure, and a hydrogen evolution curve was obtained at a scan rate of 10mV/s as shown in curve (d) of FIG. 6.

The electrochemical hydrogen evolution activity test in the embodiment of the invention comprises the following steps:

the working electrode was prepared as follows: weighing 0.10g of sample to be detected and 0.15g of graphite powder, grinding the sample to be detected and the graphite powder by using an agate mortar to obtain a fully mixed powder sample, dripping 0.1ml of silicone oil into the fully mixed powder sample, and fully stirring to obtain a paste sample with fine and uniform particles. The sample was filled into a carbon paste electrode and polished. The Pt sheet electrode was used as a counter electrode, the saturated calomel electrode was used as a reference electrode, and the electrolyte solution was KOH at a concentration of 1.0M. The LSV linear scan test was performed at room temperature and pressure, with a scan rate of 10 mV/s.

The electrocatalytic hydrogen evolution curve of the iron monatomic self-assembled molybdenum sulfide material is shown in fig. 6. In the 1.0mol/L KOH solution, when the working electrode is a graphite electrode, the potential scanning window has no catalytic current related to HER. Fe-MoS synthesized at different concentrations₂The sample showed a low overpotential of 282mV to 563mV at a current density of 10mA · cm-2. And pure MoS₂The electrode potential of the sample was then 462mV, indicating that the addition of monatomic iron significantly increased HER activity. And the optimum condition is Fe-MoS synthesized at a concentration of 1.5mol/L Fe (II)₂The overpotential of the electrode is 101mV, which is closest to the Pt/C electrode and is far less than 462mV pure MoS₂The electrode potential.

Example 24

The method comprises the following steps: MoS preparation by hydrothermal method₂. 0.010mol of sodium molybdate (Na)₂MoO₄·2H₂O) was dissolved in 30.0mL of deionized water and ultrasonically dispersed for 30 minutes. Then, thiourea [ (NH) was added in a molar ratio of 1:3 in a total amount of 0.040mol₂)₂CS]And sodium thiosulfate were co-dissolved in 30.0mL of deionized water and likewise sonicated for 30 minutes. Slowly dropwise adding the sulfur source water solution into the sodium molybdate water solution under magnetic stirring, and stirring for 1h to uniformly mix. Then the mixed solution is moved into a 100mL hydrothermal high-pressure reaction kettle and placed in a blast oven at 230 ℃ for reaction for 20 hours. After the reaction is completed, cooling to room temperature, carrying out vacuum filtration, washing with deionized water and ethanol to be neutral, and removing soluble substances. Finally, drying the finally obtained product in a vacuum drying oven at 60 ℃ for 6h to obtain MoS₂And (3) sampling.

Step two: the monatomic iron assembled molybdenum disulfide is synthesized by a thermal equilibrium method. Mixing the components in a molar ratio of 1: 1 FeSO₄·4H₂O and FeCl₂·4H₂O was co-dissolved in 30.0mL of deionized water to produce a 2.5mol/L solution. Then, 0.4g of MoS was stirred magnetically₂And dispersing in the Fe source solution for 1 h. The mixed solution was transferred to a 50mL hydrothermal autoclave and placed in a 220 ℃ forced air oven for reaction for 10 hours. After the reaction is completed, cooling to room temperature, vacuum filtering, and then using deionized water and waterWashing with ethanol to neutrality, and removing soluble substances. Drying the finally obtained product in a vacuum drying oven at 60 ℃ for 6h to obtain Fe2.5-MoS₂The sample, i.e. the sample obtained in the iron salt solution at a concentration of 1M, is as follows.

Step three: electrocatalytic hydrogen evolution. The working electrode was prepared as follows: weighing 0.10g of sample to be detected and 0.15g of graphite powder, grinding the sample to be detected and the graphite powder by using an agate mortar to obtain a fully mixed powder sample, dripping 0.1ml of silicone oil into the fully mixed powder sample, and fully stirring to obtain a paste sample with fine and uniform particles. The sample was filled into a carbon paste electrode and polished. The Pt sheet electrode was used as a counter electrode, the saturated calomel electrode was used as a reference electrode, and the electrolyte solution was KOH at a concentration of 1.0M. A linear scan test was carried out at normal temperature and pressure, and a hydrogen evolution curve was obtained at a scan rate of 10mV/s as shown in curve (e) of FIG. 6.

As shown in fig. 4, indicating the presence of molybdenum sulfide and iron in the material. Diffraction peaks of the diffraction curve (a) of molybdenum sulfide at 2 θ of 12.55 °, 33.36 °, 39.42 °, 57.28 ° and 70.14 ° correspond to diffraction crystal planes of MoS2(002), (101), (103), (110) and (108). Diffraction peaks at 14.11 °, 33.36 °, 39.42 °, 59.29 ° and 70.14 of the curve 2 θ correspond to Fe — MoS₂(002) Diffraction crystal planes of (101), (103), (110) and (108).

Fig. 5(a) -5(g) show the dispersion state of iron monoatomic atoms in the catalytic material, which indicates that the catalytic material obtained by the present embodiment has a high dispersion degree of iron monoatomic atoms, and is distributed in a highly dispersed state as a whole, and is substantially in a monoatomic state. As shown in FIGS. 2(g) and 5(g), the dispersibility of the monoatomic compound is excellent, and the monoatomic compound is dispersed on the surface of the substrate.

The foregoing descriptions of specific exemplary embodiments of the present invention have been presented for purposes of illustration and description. It is not intended to limit the invention to the precise form disclosed, and obviously many modifications and variations are possible in light of the above teaching. The exemplary embodiments were chosen and described in order to explain certain principles of the invention and its practical application to enable one skilled in the art to make and use various exemplary embodiments of the invention and various alternatives and modifications as are suited to the particular use contemplated. It is intended that the scope of the invention be defined by the claims and their equivalents.