Molybdenum sulfide-based electro-catalytic material as well as preparation method and application thereof

Abstract

The invention relates to the technical field of catalytic materials, in particular to a molybdenum sulfide-based electro-catalytic material and a preparation method and application thereof. The invention provides a molybdenum sulfide-based electro-catalytic material, which comprises a transition metal chalcogenide containing chalcogen element vacancies and titanium dioxide quantum dots containing oxygen vacancies compounded on the surface of the transition metal chalcogenide, and a composite interface of the transition metal chalcogenide and the titanium dioxide quantum dots has a heterojunction structure. According to the composite electrocatalytic hydrogen evolution catalyst containing the TiO2 quantum dots and coupled with the double vacancies and the preparation method of the composite electrocatalytic hydrogen evolution catalyst, through the quantum effect and the double vacancy defect effect of the TiO2 quantum dots, the conductivity and the active site density of transition metal chalcogenide catalysts are improved, and the electrocatalytic hydrogen evolution performance is synergistically enhanced.

Description

Technical Field

[0001] The present invention relates to the technical field of catalytic materials, and in particular to a molybdenum sulfide-based electrocatalytic material and a preparation method and application thereof. Background Art

[0002] Hydrogen energy is considered an ideal alternative to fossil fuels due to its zero carbon emissions, high energy density, and recyclability. However, as a secondary energy source, the large-scale application of hydrogen energy is highly dependent on breakthroughs in green hydrogen production technologies. Among the many hydrogen production pathways, electrocatalytic water splitting technology (2H2O→2H2+O2) has attracted much attention due to its mild reaction conditions and high product purity. However, its industrialization process is limited by the efficiency and cost of cathode hydrogen evolution reaction (HER) catalysts. Currently, although precious metal platinum (Pt)-based catalysts have excellent performance, their high price and resource scarcity have seriously restricted their large-scale application.

[0003] Transition metal dichalcogenides (TMDs), such as molybdenum sulfide, possess high melting points and hardness, excellent thermal and mechanical stability, and excellent corrosion resistance. They have been widely used in various fields such as high-temperature resistance, friction resistance, and chemical resistance. Furthermore, TMDs' graphene-like structure and excellent physicochemical properties have led to their extensive application in electrocatalytic hydrogen evolution research. Furthermore, TMDs possess electronic structures and catalytic properties similar to those of precious metals, making them widely used as catalysts for hydrogen-dependent reactions such as alkane isomerization, unsaturated hydrocarbon hydrogenation, hydrodesulfurization, and denitrogenation. Their catalytic performance rivals that of the precious metals platinum and iridium, making them promising electrocatalysts known as "platinum-like catalysts." However, the catalytic activity of natural MoS2 is highly dependent on its edge sulfur vacancies. The basal plane, dominated by the inert 2H phase, results in an insufficient active site density. Furthermore, their intrinsic semiconductor properties result in inefficient charge transfer, severely limiting further improvements in catalytic performance.

[0004] Titanium dioxide (TiO2) is a classic support for the water-gas shift reaction (WGS; H2O + CO → H2 + CO2). Its role is to activate the decomposition reactant water (H2O), a property that is similar to the initial step of the electrocatalytic water decomposition hydrogen evolution reaction. However, the insulating nature of bulk TiO2 limits charge transport. In contrast, TiO2 quantum dots (TiO2QDs) have a quantum effect that can significantly improve their conductivity and form an atomic-level heterojunction interface with the HER catalyst through the low-coordinated Ti sites on the surface. This interfacial effect induces lattice distortion on the catalyst basal plane, exposing more intrinsic active sites.

[0005] Therefore, combining transition metal chalcogenides and titanium dioxide may improve the hydrogen evolution performance of a single material to solve the problems of low hydrogen evolution efficiency and production capacity of existing materials. Summary of the Invention

[0006] The present invention provides a molybdenum sulfide-based electrocatalytic material, its preparation method, and its application. The molybdenum sulfide-based electrocatalytic material prepared by this method contains a synergistic crystalline heterojunction of S and O vacancies, which increases the number of reactive sites and effectively improves the electrocatalytic hydrogen production performance of a single-component TiO2 / transition metal chalcogenide compound.

[0007] In order to achieve the above object, the present invention provides the following technical solutions:

[0008] The present invention provides a molybdenum sulfide-based electrocatalytic material, comprising a transition metal sulfide compound containing sulfide element vacancies and titanium dioxide quantum dots containing oxygen vacancies composited on the surface of the transition metal sulfide compound, wherein the composite interface of the two has a heterojunction structure.

[0009] The present invention utilizes TiO2 QDs as a highly efficient hydrogen evolution catalyst, leveraging their advantages of small size, quantum effects, and short electron transport pathways. Furthermore, the formation of divacancy coupled with the quantum effect ensures the catalyst's excellent electrical conductivity. The abundant contact surface between TiO2 QDs and transition metal chalcogenides forms a sufficient heterogeneous interface, promoting efficient interfacial charge transfer and facilitating the hydrogen evolution reaction.

[0010] Specifically, the present invention combines transition metal chalcogenides with TiO2 quantum dots, utilizing the small size effect of quantum dots (2 to 10 nm) to shorten the carrier migration path, and induces the lattice distortion of the basal plane of the transition metal chalcogenides through strong electronic coupling at the interface, thereby activating its intrinsic inert region. Furthermore, a hydrogen reduction process is used to simultaneously realize the construction of oxygen vacancies in TiO2 and chalcogen vacancies in the transition metal chalcogenides during high-temperature calcination: hydrogen molecules penetrate into the TiO2 lattice and selectively remove oxygen atoms to form oxygen vacancies, significantly improving the conductivity of the material; at the same time, hydrogen atoms react with chalcogen atoms in the transition metal chalcogenides to generate H2X (X is S, Se, or Te) and desorb, precisely constructing chalcogen vacancies on the basal plane. This double-defect synergistic effect not only optimizes the charge transfer efficiency of the heterogeneous interface, but also regulates the H* adsorption free energy through the electronic interaction between oxygen vacancies and chalcogen vacancies, making the HER activity of the composite catalyst significantly surpass that of a single component.

[0011] Preferably, the chalcogen vacancy is a sulfur vacancy, a selenium vacancy or a tellurium vacancy.

[0012] Preferably, in the transition metal chalcogenide compound, the transition metal is Mo, W or Re, and the chalcogen element is S, Se or Te.

[0013] Preferably, the transition metal chalcogenide is MoS2, MoSe2, MoTe2, WTe2, WS2 or WSe2.

[0014] Preferably, the MoS2 is in 1T phase and / or 2H phase.

[0015] The present invention provides a method for preparing a molybdenum sulfide-based electrocatalytic material, comprising:

[0016] S1. Preparation of transition metal chalcogenides;

[0017] S2. The transition metal sulfide compound is mixed with a titanium source and urea and then hydrothermally treated to obtain a transition metal sulfide compound and titanium dioxide quantum dot heterojunction material; under a reducing atmosphere, the transition metal sulfide compound and titanium dioxide quantum dot heterojunction material are annealed and reduced to obtain a transition metal sulfide compound containing sulfur element vacancies and a titanium dioxide quantum dot heterojunction material containing oxygen vacancies, namely, a molybdenum sulfide-based electrocatalytic material.

[0018] The present invention first prepares a transition metal chalcogenide compound, then puts it into the preparation process of TiO2 QDs, obtains a heterojunction material by hydrothermal treatment, and then anneals and reduces it to form divacancies on the heterojunction material.

[0019] The solution provided by the present invention can simultaneously achieve the regulation of the formation of oxygen vacancies in defective black TiO2 and the chalcogen vacancies of transition metal chalcogen compounds through hydrogen reduction. During the reduction process, the TiO2 lattice captures hydrogen to form oxygen vacancies (V O ), transforming into metallic black titanium dioxide (TiO 2-x ), and the transition metal chalcogenide basal plane forms a chalcogen vacancy (Vx, X is S, Se or Te) through the removal of chalcogen atoms (S, Se or Te). This double-defect heterojunction produces a dual synergistic effect: first, oxygen vacancies give TiO 2-x High conductivity, accelerating interfacial charge transfer; secondly, chalcogen vacancies increase the active site density of transition metal chalcogenides and optimize H* adsorption energy. More importantly, the present invention utilizes the advantages of TiO2 QDs such as small size, quantum effect, short electron transmission path, and good conductivity, effectively solving the bottleneck problem that traditional TiO2 bulk catalysts cannot be used for electrocatalysis due to poor conductivity. In addition, the abundant contact surface between TiO2 QDs and transition metal chalcogenides forms a sufficient heterogeneous interface, which will also promote the efficient transmission of interfacial charges and promote hydrogen evolution reaction. The quantum effect of TiO2 QDs will also improve the electronic structure of the heterogeneous interface, promote the rearrangement of the electronic structure, activate the active sites, and promote the hydrogen evolution reaction.

[0020] Furthermore, compared with the traditional high-temperature hydrogen reduction method, the present invention simultaneously achieves heterostructure construction and dual-defect regulation through a one-step high-temperature calcination, greatly simplifying the process flow and reducing energy consumption, providing a new solution for the large-scale preparation of high-efficiency HER catalysts.

[0021] Preferably, the size of the titanium dioxide quantum dots is 2 to 10 nm.

[0022] Preferably, in S1, the transition metal source and the chalcogen source are dissolved and then subjected to a hydrothermal reaction to obtain a transition metal chalcogen compound.

[0023] Preferably, the transition metal source is a molybdenum salt, a tungsten salt or a rhenium salt.

[0024] Preferably, the molybdenum salt comprises ammonium molybdate and / or ammonium tetrathiomolybdate.

[0025] Preferably, the chalcogen source is a sulfur source, a selenium source or a tellurium source.

[0026] Preferably, the sulfur source comprises at least one of thiourea, thioacetamide or L-cysteine.

[0027] Preferably, in the hydrothermal reaction, the temperature is 180-200° C. and the time is 18-24 h.

[0028] Preferably, the dissolving solvent is at least one of deionized water, ethanol, methanol, and N,N-dimethylformamide.

[0029] Preferably, after the hydrothermal reaction, the transition metal chalcogenide is obtained by washing, removing impurities and drying. More preferably, the washing reagent is deionized water and / or ethanol.

[0030] Preferably, in S2, the hydrothermal temperature is 180-200° C., and the hydrothermal time is 3-6 h.

[0031] Preferably, in S2, the titanium source is a titanium salt. More preferably, the titanium source includes titanium sulfate.

[0032] Preferably, in S2, the molar ratio between the transition metal chalcogenide and the titanium in the titanium source is (3-30):1.

[0033] Preferably, in S2, the molar ratio between the transition metal chalcogenide and the titanium in the titanium source is (8-20):1.

[0034] Preferably, in S2, the transition metal chalcogenide, the titanium source, and urea are mixed in a solvent. More preferably, the solvent comprises deionized water.

[0035] Preferably, in S2, the mixing method is ultrasonic mixing. More preferably, the ultrasonic mixing time is 10 to 30 minutes.

[0036] Preferably, in S2, the hydrothermal step is followed by washing and impurity removal, followed by drying to obtain the transition metal chalcogenide and titanium dioxide quantum dot heterojunction material. More preferably, the washing agent is deionized water and / or ethanol.

[0037] Preferably, the S2 reducing atmosphere is a hydrogen-containing atmosphere.

[0038] Preferably, the S2 reducing atmosphere is at least one of hydrogen, a hydrogen-nitrogen mixture, and a hydrogen-inert gas mixture. More preferably, the inert gas comprises argon.

[0039] Preferably, the hydrogen content in the S2 reducing atmosphere is ≥10v%.

[0040] Preferably, in S2, the annealing reduction temperature is 500-800°C, and the time is ≥1h.

[0041] Preferably, in S2, the annealing reduction temperature is 500-700° C., and the time is 1-3 h.

[0042] Preferably, in S2, during annealing reduction, the heating rate is 5-10°C / min.

[0043] The present invention also provides the application of molybdenum sulfide-based electrocatalytic materials as HER catalysts.

[0044] Preferably, it is used as a HER catalyst for water electrolysis to produce hydrogen and / or batteries.

[0045] Preferably, the battery is a Zn-H2O battery, more preferably a diaphragmless Zn-H2O battery.

[0046] A HER catalytic electrode includes a molybdenum sulfide-based electrocatalytic material.

[0047] A device containing a HER catalytic electrode is a water electrolysis hydrogen production device and / or a battery.

[0048] Preferably, the battery is a Zn-H2O battery, more preferably a diaphragmless Zn-H2O battery.

[0049] Therefore, the present invention has the following beneficial effects:

[0050] (1) The present invention provides a new composite electrocatalytic hydrogen evolution catalyst containing TiO2 quantum dots coupled with divacancy and a preparation method thereof. Through the quantum effect of TiO2 quantum dots and the divacancy defect effect, the conductivity and active site density of transition metal sulfide compound catalysts such as MoS2 are improved, and the electrocatalytic hydrogen evolution performance is synergistically enhanced.

[0051] (2) This invention uses low-cost raw materials such as titanium sulfate and molybdenum source, combined with a mature hydrothermal method and tubular furnace annealing process, and has good scalability. This strategy can also be extended to TiO2 QDs@MoSe2, TiO2 QDs@WS2, TiO2QDs@WSe2 and other systems, providing a universal template for the development of multi-element high-efficiency catalysts. BRIEF DESCRIPTION OF THE DRAWINGS

[0052] Figure 1 A comparison chart of catalytic performance. DETAILED DESCRIPTION

[0053] The present invention will be further described below with reference to specific embodiments. Those skilled in the art will be able to implement the present invention based on these descriptions. Furthermore, the embodiments of the present invention described below generally represent only a portion of the present invention, rather than all of the embodiments. Therefore, all other embodiments derived by those skilled in the art based on the embodiments of the present invention without inventive effort should fall within the scope of protection of the present invention.

[0054] [Example]

[0055] Example 1 Oxygen-sulfur divacancy TiO2 QDs@MoS2

[0056] (1) MoS2 preparation: Accurately weigh 0.206 g of ammonium molybdate tetrahydrate ((NH4)6Mo7O 24 4H2O) and 0.3806g of thiourea (CH4N2S) were dissolved in 30mL of deionized water under magnetic stirring to form a homogeneous solution. The solution was then transferred to a 50mL Teflon-lined stainless steel autoclave. The autoclave was placed in a 200°C electric furnace and reacted for 18 hours before cooling to room temperature. The final product was washed several times with deionized water and anhydrous ethanol to remove any possible ions and then air-dried at room temperature to obtain 1T phase MoS2.

[0057] (2) Preparation of TiO2 QDs@MoS2 with oxygen and sulfur divacancy: 0.252 g (1 mmol) of anhydrous titanium sulfate, 1.601 g (10 mmol) of prepared molybdenum disulfide, and 0.0063 g (0.1 mmol) of urea were weighed and dissolved in 70 mL of deionized water. The solution was then stirred and ultrasonicated for 15 min. The resulting mixture was hydrothermally treated at 170 ° C for 4 h in a 100 mL Teflon-lined stainless steel autoclave. Finally, the final product was washed several times with deionized water. The product was then placed in a tube furnace and annealed at 550 ° C for 1 h using argon containing 10% hydrogen (10% H2-Ar) as the carrier gas to obtain the final product.

[0058] Comparative Example 1 MoS2

[0059] Accurately weigh 0.206g of ammonium molybdate tetrahydrate ((NH4)6Mo7O 24 4H2O) and 0.3806g of thiourea (CH4N2S) were dissolved in 30mL of deionized water under magnetic stirring to form a homogeneous solution. The solution was then transferred to a 50mL Teflon-lined stainless steel autoclave. The autoclave was placed in a 200°C electric furnace and reacted for 18 hours before cooling to room temperature. The final product was washed several times with deionized water and anhydrous ethanol to remove any possible ions and then air-dried at room temperature to obtain 1T phase MoS2.

[0060] Comparative Example 2 TiO2 QDs@MoS2 reflux composite

[0061] (1) MoS2 preparation: Accurately weigh 0.206 g of ammonium molybdate tetrahydrate ((NH4)6Mo7O 24 4H2O) and 0.3806g of thiourea (CH4N2S) were dissolved in 30mL of deionized water under magnetic stirring to form a homogeneous solution. The solution was then transferred to a 50mL Teflon-lined stainless steel autoclave. The autoclave was placed in a 200°C electric furnace and reacted for 18 hours before cooling to room temperature. The final product was washed several times with deionized water and anhydrous ethanol to remove any possible ions and then air-dried at room temperature to obtain 1T phase MoS2.

[0062] (2) Preparation of TiO2 QDs@MoS2: 30 mL of cyclohexane and 30 mL of anhydrous ethanol were mixed and stirred at 25°C for 10 min. After mixing evenly, 0.25 mL (0.71 mmol) of tetrabutyl titanate and 1.15 g (7.1 mmol) of prepared molybdenum disulfide were added and stirring continued for 30 min. 0.125 mL of hydrochloric acid was added to the above solution, and the resulting mixture was transferred to a 250 mL three-necked flask. The condenser was refluxed in a 70°C water bath for 10 h, and then anhydrous ethanol was added to the mouth of the three-necked flask to reduce the temperature to natural room temperature. The material was centrifuged at 10,000 rpm for 15 min, washed, and finally dried to obtain the product.

[0063] Comparative Example 3 TiO2 QDs@MoS2

[0064] (1) MoS2 preparation: Accurately weigh 0.206 g of ammonium molybdate tetrahydrate ((NH4)6Mo7O 244H2O) and 0.3806g of thiourea (CH4N2S) were dissolved in 30mL of deionized water under magnetic stirring to form a homogeneous solution. The solution was then transferred to a 50mL Teflon-lined stainless steel autoclave. The autoclave was placed in a 200°C electric furnace and reacted for 18 hours before cooling to room temperature. The final product was washed several times with deionized water and anhydrous ethanol to remove any possible ions and then air-dried at room temperature to obtain 1T phase MoS2.

[0065] (2) Preparation of TiO2 QDs@MoS2: 0.252 g (1 mmol) of anhydrous titanium sulfate, 1.601 g (10 mmol) of prepared molybdenum disulfide, and 0.0063 g (0.1 mmol) of urea were dissolved in 70 mL of deionized water. The solution was then stirred and sonicated for 15 min. The resulting mixture was hydrothermally treated at 170°C for 4 h in a 100 mL Teflon-lined stainless steel autoclave. The final product was washed several times with deionized water.

[0066]

Performance test

[0067] Catalytic Performance Testing: Linear sweep voltammetry (LSV) was performed using a CHI660E electrochemical workstation with the following parameters: Init E = -0.159 V, Final E = 0.659 V, Scan Rate = 0.005 V / s, Sample Interval = 0.001 V, Quiet Time = 2, and Sensitivity = 1.e-002 A / V. The electrolyte was 1 M potassium hydroxide (KOH) solution, and a saturated calomel electrode (SCE) and a carbon rod served as the reference and counter electrodes, respectively. Linear sweep voltammetry (LSV) scans were performed with the following parameters: Init E = -0.784 V, Final E = -1.684 V, Scan Rate = 0.005 V / s, Sample Interval = 0.001 V, Quiet Time = 2, and Sensitivity = 1.e-002 A / V.

[0068] The final products obtained in Example 1 and Comparative Examples 1 to 3 were tested according to the above catalytic performance test method. The results are as follows: Figure 1 As shown. In order to confirm the effect of TiO2 QDs and divacancy on electrocatalytic performance, polarization curves were carried out in alkaline medium to evaluate HER performance. Polarization curves were carried out in 1M KOH to estimate HER activity. Figure 1 As shown, the 1T phase MoS2 (Comparative Example 1) without any treatment is -2 (η 10 ) is 318mV, while the current density of Comparative Example 2 is 318mV at η 10The overpotential is only 287 mV, which is a decrease of 31 mV, indicating that TiO2 QDs have a certain promoting effect on HER performance.

[0069] Furthermore, the η of Comparative Example 3 (249mV) 10 It is 38 mV lower than that of comparative example 2 (287 mV), which indicates that the TiO2 DQs formed by the hydrothermal method can produce more active sites than the reflux method, thereby improving the HER performance of the composite catalytic material (TiO2QDs@MoS2) in alkaline medium.

[0070] More notably, the η of the TiO2 QDs@MoS2 catalyst (Example 1) reduced by hydrogen 10 This is significantly lower than that of Comparative Example 3, indicating that the TiO2 oxygen vacancies and MoS2 sulfur vacancies formed during hydrogen reduction further enhance the active sites and significantly improve the HER performance. In short, in the order of Comparative Example 1, Comparative Example 2, Comparative Example 3, and Example 1, the overpotential gradually decreases from 318 mV to 155 mV under the regulation of quantum effects, heterostructures, and oxygen and sulfur vacancies.

Claims

1. A molybdenum sulfide-based electrocatalytic material, characterized in that: The invention comprises a transition metal chalcogenide compound containing chalcogenide vacancies and titanium dioxide quantum dots containing oxygen vacancies compounded on the surface of the transition metal chalcogenide compound, and the composite interface of the two has a heterojunction structure.

2. The molybdenum sulfide-based electrocatalytic material according to claim 1, wherein The chalcogen vacancy is a sulfur vacancy, a selenium vacancy or a tellurium vacancy; Preferably, in the transition metal chalcogenide compound, the transition metal is Mo, W or Re, and the chalcogen element is S, Se or Te; Preferably, the transition metal chalcogenide is MoS2, MoSe2, MoTe2, WTe2, WS2 or WSe2; Preferably, the MoS2 is in 1T phase and / or 2T phase.

3. The method for preparing a molybdenum sulfide-based electrocatalytic material according to claim 1 or 2, wherein: include: S1. Preparation of transition metal chalcogenides; S2. The transition metal chalcogenide is mixed with a titanium source and urea and then hydrothermally prepared to obtain a transition metal chalcogenide and titanium dioxide quantum dot heterojunction material; under a reducing atmosphere, the transition metal chalcogenide and titanium dioxide quantum dot heterojunction material is annealed and reduced to obtain a transition metal chalcogenide containing a chalcogen element vacancy and a titanium dioxide quantum dot heterojunction material containing an oxygen vacancy, i.e., a molybdenum sulfide-based electrocatalytic material; Preferably, the size of the titanium dioxide quantum dots is 2 to 10 nm.

4. The preparation method according to claim 3, wherein In S1, a transition metal source and a chalcogen source are dissolved and then subjected to a hydrothermal reaction to obtain a transition metal chalcogen compound; Preferably, the transition metal source is a molybdenum salt, a tungsten salt or a rhenium salt; Preferably, the molybdenum salt comprises ammonium molybdate and / or ammonium tetrathiomolybdate; Preferably, the chalcogen source is a sulfur source, a selenium source or a tellurium source; Preferably, the sulfur source comprises at least one of thiourea, thioacetamide or L-cysteine; Preferably, in the hydrothermal reaction, the temperature is 180-200° C. and the time is 18-24 h; Preferably, the solvent for dissolving is at least one of deionized water, ethanol, methanol, and N,N-dimethylformamide; Preferably, after the hydrothermal reaction, the mixture is washed to remove impurities and then dried to obtain the transition metal chalcogenide compound; preferably, the washing reagent is deionized water and / or ethanol.

5. The preparation method according to claim 3, wherein In S2, the hydrothermal temperature is 180-200°C and the hydrothermal time is 3-6 hours; Preferably, in S2, the titanium source is a titanium salt; preferably, the titanium source includes titanium sulfate; Preferably, in S2, the molar ratio between the transition metal chalcogenide and the titanium in the titanium source is (3-30):1; Preferably, in S2, the molar ratio between the transition metal chalcogenide and the titanium in the titanium source is (8-20):1; Preferably, in S2, the mixing method is to mix the transition metal chalcogenide, the titanium source, and the urea in a solvent; preferably, the solvent includes deionized water; Preferably, in S2, the mixing method is ultrasonic mixing; preferably, the ultrasonic mixing time is 10 to 30 minutes; Preferably, in S2, after hydrothermal treatment, the mixture is washed to remove impurities and then dried to obtain the transition metal chalcogenide compound and titanium dioxide quantum dot heterojunction material; preferably, the cleaning reagent is deionized water and / or ethanol.

6. The preparation method according to claim 3, wherein S2 reducing atmosphere is a hydrogen-containing atmosphere; Preferably, the S2 reducing atmosphere is at least one of hydrogen, a hydrogen-nitrogen mixture, and a hydrogen-inert gas mixture; preferably, the inert gas includes argon; Preferably, the hydrogen content in the S2 reducing atmosphere is ≥10v%.

7. The preparation method according to claim 3, wherein In S2, the annealing reduction temperature is 500-800°C and the time is ≥1h; Preferably, in S2, the annealing reduction temperature is 500-700° C., and the time is 1-3 h; Preferably, in S2, during annealing reduction, the heating rate is 5-10°C / min.

8. Use of the molybdenum sulfide-based electrocatalytic material according to any one of claims 1 to 2 or the molybdenum sulfide-based electrocatalytic material prepared by the preparation method according to any one of claims 3 to 7, characterized in that: Use it as a HER catalyst; Preferably, it is used as a HER catalyst for water electrolysis to produce hydrogen and / or batteries; Preferably, the battery is a Zn-H2O battery, more preferably a diaphragm-less Zn-H2O battery.

9. A HER catalytic electrode, characterized in that The invention comprises the molybdenum sulfide-based electrocatalytic material according to any one of claims 1 to 2 or the molybdenum sulfide-based electrocatalytic material prepared by the preparation method according to any one of claims 3 to 7.

10. A device comprising the HER catalytic electrode according to claim 9, characterized in that: A device and / or battery for producing hydrogen by electrolysis of water; Preferably, the battery is a Zn-H2O battery, more preferably a diaphragm-less Zn-H2O battery.

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