Small organic molecule for improving hydrogen evolution performance of molybdenum sulfide-based catalyst, molybdenum sulfide-based catalyst and preparation method and application of molybdenum sulfide-based catalyst

Abstract

The invention belongs to the technical field of catalyst preparation, and particularly relates to a small organic molecule for improving the hydrogen evolution performance of a molybdenum sulfide-based catalyst, the molybdenum sulfide-based catalyst, a preparation method and application. The end groups at the two ends of the small organic molecule respectively comprise positive ions and negative ions; the anions comprise at least one of carboxylate ions, sulfonate ions and phosphate ions; the cations have a specific structural formula. The small organic molecule can improve the water electrolysis hydrogen evolution performance of the existing molybdenum sulfide catalyst, especially hydrogen production by alkaline water electrolysis.

Description

Technical Field

[0001] The present invention belongs to the technical field of catalyst preparation, and particularly relates to an organic small molecule, a molybdenum sulfide-based catalyst, a preparation method and an application for improving the hydrogen evolution performance of a molybdenum sulfide-based catalyst. Background Art

[0002] The molybdenum sulfide catalyst theoretically has a relatively excellent adsorption hydrogen binding energy, which is relatively close to that of the noble metal platinum, and has the potential to become an efficient hydrogen evolution catalyst. Moreover, the molybdenum sulfide-based catalyst has a simple preparation process, rich reserves and low price. However, in the face of the increasing demand for catalysts with high-efficiency hydrogen evolution performance, the molybdenum sulfide catalyst still has certain limitations.

[0003] The existing technologies for improving the performance of molybdenum sulfide in electrolytic water hydrogen production generally include creating defects, constructing heterojunctions, etc., but these methods have limited hydrogen evolution performance for MoS2-based catalysts, especially in alkaline conditions, which are far from meeting the industrial standards. Summary of the Invention

[0004] Therefore, the technical problem to be solved by the present invention is to overcome the defects such as the hydrogen evolution performance of the existing molybdenum sulfide catalyst needs to be further improved, so as to provide an organic small molecule, a molybdenum sulfide-based catalyst, a preparation method and an application for improving the hydrogen evolution performance of a molybdenum sulfide-based catalyst.

[0005] For this purpose, the present invention provides the following technical solutions.

[0006] The present invention provides an organic small molecule for improving the hydrogen evolution performance of a molybdenum sulfide-based catalyst, wherein the end groups at both ends of the organic small molecule respectively include a cation and an anion; the anion includes at least one of a carboxylate ion, a sulfonate ion and a phosphate ion; the cation has at least one of the following structural formulas:

[0007]

[0008] Further, the organic small molecule has one of the following structural formulas:

[0009]

[0010] Wherein, n is 1-12. Exemplarily, the value of n is 1, 3, 6, 8, 10, 12 or any value within this range.

[0011] Further, the organic small molecule has one of the following structural formulas:

[0012]

[0013] And / or

[0014] where n is 1 - 5.

[0015] The present invention also provides a molybdenum sulfide - based catalyst, the molybdenum sulfide - based catalyst includes molybdenum sulfide, the molybdenum sulfide includes 1T phase; the molybdenum sulfide - based catalyst includes quaternary ammonium groups, and also includes at least one of carboxyl groups, sulfonic acid groups and phosphoric acid groups.

[0016] Further, the molybdenum sulfide - based catalyst includes doped metals, the doped metals include transition metals and / or noble metals; and / or,

[0017] The molybdenum sulfide - based catalyst further includes a carrier.

[0018] Further, the doped metals include at least one of nickel, iron, cobalt, platinum, ruthenium; and / or,

[0019] The carrier includes carbon nanotubes, graphene or carbon fiber.

[0020] The present invention provides a preparation method of a molybdenum sulfide - based catalyst, including hydrothermal reaction after mixing a molybdenum source and an organic small molecule; the end groups at both ends of the organic small molecule respectively include a cation and an anion, the anion includes at least one of carboxylate ions, sulfonate ions and phosphate ions, and the cation has at least one of the following structural formulas:

[0021]

[0022] Further, when performing the mixing, a sulfur source and / or a doped metal source are also included; and / or,

[0023] When performing the mixing, a carrier is also included, the carrier includes carbon nanotubes, graphene or carbon fiber; preferably, the mass ratio of the carrier to the molybdenum source is 1:(6 - 10); and / or,

[0024] The temperature of the hydrothermal reaction is 170 - 220 °C, and the time is 6 - 20 h; and / or,

[0025] The organic small molecule has one of the following structural formulas:

[0026]

[0027] where n is 1 - 12.

[0028] Further, the molybdenum source includes molybdate and / or ammonium heptamolybdate; preferably, the ammonium heptamolybdate includes (NH4)6Mo7O 24 ; the molybdate includes at least one of (NH4)2MoO4, Na2MoO4 and K2MoO4; and / or,

[0029] The sulfur source includes sulfur-containing compounds. Preferably, the sulfur-containing compounds include at least one of thiourea, thioether, and thioacetamide; and / or,

[0030] The metal in the doped metal source includes at least one of nickel, iron, cobalt, platinum, and ruthenium; and / or,

[0031] The doped metal source is a water-soluble salt of the doped metal; and / or,

[0032] The molar ratio of molybdenum in the molybdenum source, the doped metal in the doped metal source, the organic small molecule and the sulfur source is 1:(0.05 - 0.2):(0.1 - 0.5):(2 - 4); and / or,

[0033] The molar ratio of molybdenum in the molybdenum source, the organic small molecule and the sulfur source is 1:(0.1 - 0.5):(2 - 4).

[0034] Furthermore, the organic small molecule has one of the following structural formulas:

[0035]

[0036] wherein, n is 1 - 12.

[0037] The doped metal source is a water-soluble salt of the doped metal. Specifically, the nickel source includes water-soluble nickel salts, and the nickel source includes at least one of nickel sulfate, nickel nitrate, or nickel chloride. The iron source includes water-soluble iron salts, including divalent iron salts and trivalent iron salts; the divalent iron salts include at least one of ferrous chloride, ferrous sulfate, or ferrous nitrate; the trivalent iron salts include at least one of ferric chloride, ferric sulfate, or ferric nitrate. The cobalt source includes water-soluble cobalt salts, and the water-soluble cobalt salts include at least one of cobalt chloride, cobalt sulfate, or cobalt nitrate. The platinum source includes soluble platinum sources, such as H2PtCl6·(H2O)6. The ruthenium source includes soluble ruthenium salts, such as RuCl3·3H2O.

[0038] It should be noted that before the hydrothermal reaction, various components need to be dissolved with water as the solvent. The amount of water added is a well-known amount in the art and can be obtained according to actual needs. The present invention does not limit the amount of water added.

[0039] The present invention provides an application of the above molybdenum sulfide-based catalyst in electrolytic water hydrogen evolution.

[0040] The technical solution of the present invention has the following advantages:

[0041] 1. The organic small molecule provided by the present invention for improving the hydrogen evolution performance of molybdenum sulfide-based catalysts has end groups at both ends, which respectively include a cation and an anion; the anion includes at least one of carboxylate ions, sulfonate ions, and phosphate ions; the cation has a specific structural formula. This organic small molecule can improve the hydrogen evolution performance of existing molybdenum sulfide catalysts in electrolytic water, especially in alkaline electrolytic water hydrogen production, including but not limited to liquid alkaline water electrolysis (AWE), anion exchange membrane water electrolysis (AEMWE), and proton exchange membrane water electrolysis (PEMWE). The surface of the molybdenum sulfide catalyst is modified with the organic small molecule of the present invention, enabling molybdenum sulfide to form a 1T phase with better conductivity, reducing the overpotential, increasing the current density, and improving the hydrogen evolution performance of the catalyst. Further, the organic small molecule provided by the present invention has a significant promoting effect on the hydrogen evolution performance of both 2H-phase and 1T-phase molybdenum sulfide catalysts. The anion end of the organic small molecule mainly serves as an anchoring group, coordinating with metal cations in the molybdenum sulfide-based catalyst, such as molybdenum ions, etc., to fix the small molecule on the surface of molybdenum sulfide. The cation end is the functional end, which improves the hydrogen bond network of interfacial water, promotes water dissociation, and enhances the hydrogen evolution performance of the catalyst.

[0042] 2. The molybdenum sulfide-based catalyst provided by the present invention includes a quaternary ammonium group, which helps molybdenum sulfide form a 1T phase with better conductivity, resulting in a lower overpotential and a higher current density of the catalyst, and better hydrogen evolution performance.

[0043] 3. The preparation method of the molybdenum sulfide-based catalyst provided by the present invention uses a molybdenum source and an organic small molecule as raw materials. When preparing the molybdenum sulfide-based catalyst, it helps to form a 1T phase with better conductivity, a lower overpotential, a higher current density, and better hydrogen evolution performance of the catalyst. The organic small molecule of the present invention can improve the hydrogen evolution performance of any molybdenum sulfide-based catalyst, including catalysts such as molybdenum sulfide, doped molybdenum sulfide, and supported molybdenum sulfide.

[0044] 4. In the preparation method of the molybdenum sulfide-based catalyst provided by the present invention, the doped metal and metal molybdenum act synergistically to further improve the hydrogen evolution performance of molybdenum sulfide. Sulfur-containing compounds such as thiourea mainly provide a sulfur source for the catalyst. Carriers such as graphene and carbon nanotubes have better conductivity and can enhance the overall conductivity of the catalyst. BRIEF DESCRIPTION OF THE DRAWINGS

[0045] In order to more clearly illustrate the specific embodiments of the present invention or the technical solutions in the prior art, the following will briefly introduce the drawings required for use in the description of the specific embodiments or the prior art. Obviously, the drawings in the following description are some embodiments of the present invention. For those of ordinary skill in the art, other drawings can be obtained based on these drawings without creative efforts.

[0046] Figure 1It is a schematic diagram of the hydrophilicity and hydrophobicity of the molybdenum sulfide catalyst in Example 1 and Control Group 1 of the present invention;

[0047] Figure 2 It is an SEM image of the molybdenum sulfide catalyst in Example 1 and Control Group 1 of the present invention;

[0048] Figure 3 It is an XRD pattern of the molybdenum sulfide catalyst in Example 1 and Control Group 1 of the present invention;

[0049] Figure 4 It is an energy-dispersive X-ray spectroscopy diagram of the molybdenum sulfide catalyst in Example 1 of the present invention;

[0050] Figure 5 It is a linear sweep voltammetry (LSV) curve of the molybdenum sulfide catalyst in Example 1 and Control Group 1 of the present invention;

[0051] Figure 6 It is an LSV curve of the molybdenum sulfide catalyst in Example 2 and Control Group 2 of the present invention;

[0052] Figure 7 It is an LSV curve of the molybdenum sulfide catalyst in Example 3 and Control Group 3 of the present invention;

[0053] Figure 8 It is an LSV curve of the molybdenum sulfide catalyst in Example 4 and Control Group 4 of the present invention;

[0054] Figure 9 It is an LSV curve of the molybdenum sulfide catalyst in Example 5 and Control Group 5 of the present invention;

[0055] Figure 10 It is an LSV curve of the molybdenum sulfide catalyst in Example 6 and Control Group 6 of the present invention;

[0056] Figure 11 It is an LSV curve of the molybdenum sulfide catalyst in Example 7 and Comparative Example 1 of the present invention. Detailed implementation manners

[0057] The following examples are provided to better further understand the present invention. They are not limited to the best implementation manner, and do not constitute a limitation to the content and protection scope of the present invention. Any product that is the same as or similar to the present invention obtained by anyone under the inspiration of the present invention or by combining the features of the present invention with those of other existing technologies falls within the protection scope of the present invention.

[0058] For those not specifying specific experimental steps or conditions in the examples, the operations or conditions of the conventional experimental steps described in the literature in this field can be followed. For reagents or instruments not specifying the manufacturer, they are all conventional reagent products that can be obtained through commercial purchase.

[0059] Example 1

[0060] This embodiment provides a method for preparing a molybdenum sulfide-based catalyst, comprising the following steps:

[0061] (NH4)2MoO4, nickel nitrate, organic small molecule A and thiourea are mixed in a molar ratio of 1:0.05:0.5:2.5, and water is added to make a mixed solution; hydrothermal reaction is carried out at 220 °C for 15 h to obtain a Ni-MoS2 catalyst.

[0062] Among them, the preparation method of organic small molecule A includes: reacting trimethylamine and bromopropionic acid in isopropanol, generating a precipitate after stirring and heating under reflux at 90 °C, and then filtering, washing and drying to obtain organic small molecule A. The reaction process and the structural formula of organic small molecule A are as follows:

[0063]

[0064] Based on this embodiment, the molybdenum sulfide-based catalyst obtained without adding organic small molecules is used as Control Group 1.

[0065] Figure 1 is a schematic diagram of the hydrophilicity and hydrophobicity of the molybdenum sulfide catalysts of Example 1 and Control Group 1, obtained by a contact angle measuring instrument. a is the catalyst of Control Group 1, and b is the catalyst of Example 1. It can be seen from the figure that the surface of the catalyst in Control Group 1 is hydrophobic, and the surface of the catalyst of Example 1 obtained by modifying with organic small molecules is hydrophilic, and the hydrophilicity is greatly improved, which is beneficial to improving the mass transfer efficiency between water and the catalyst during the electrolysis of water to produce hydrogen, is beneficial to the bubble detachment, enables hydrogen to quickly detach from the catalyst, improves the contact between water and the catalyst, and thus is beneficial to improving the electrolysis of water to produce hydrogen.

[0066] Figure 2 is the SEM image of the molybdenum sulfide catalysts of Example 1 and Control Group 1. a is the catalyst of Control Group 1, and b is the catalyst of Example 1. From Figure 2 it can be seen that adding organic small molecules converts MoS2 from the 2H phase to the 1T phase. The 1T phase MoS2 has better conductivity, which is beneficial to improving the electron transfer efficiency, reducing the internal resistance of the catalyst, increasing the current density, and further improving the hydrogen evolution performance of the electrolysis of water.

[0067] Figure 3 is the XRD pattern of the molybdenum sulfide catalysts of Example 1 and Control Group 1. It can be seen from the figure that after introducing organic small molecules into molybdenum sulfide, molybdenum sulfide changes from the 2H phase to the 1T phase. Among them, Ni-MoS2-Z is the XRD pattern of the molybdenum sulfide catalyst of Example 1, and Ni-MoS2 is the XRD pattern of the molybdenum sulfide catalyst of Control Group 1.

[0068] Figure 4It is the energy-dispersive X-ray spectrogram of the molybdenum sulfide catalyst in Example 1. It can be seen from the figure that the molybdenum sulfide-based catalyst synthesized in Example 1 contains elements such as Mo, Ni, S, N, and O, and the distribution of each element is uniform, indicating that the doped Ni is uniformly dispersed in MoS2. N and O mainly come from organic small molecules, which can prove that the organic small molecules are successfully modified on the surface of MoS2 and are uniformly distributed.

[0069] Example 2

[0070] This example provides a preparation method of a molybdenum sulfide-based catalyst. The difference from Example 1 is that ferrous sulfate is used instead of nickel nitrate, and the molar amount of iron in ferrous sulfate is the same as the molar amount of nickel in nickel nitrate; organic small molecule B is used to replace organic small molecule A in an equimolar amount to obtain an Fe-MoS2 catalyst.

[0071] Among them, the synthesis method of organic small molecule B is the same as that of organic small molecule A in Example 1. The structural formula of organic small molecule B is as follows:

[0072]

[0073] The molybdenum sulfide-based catalyst obtained without adding organic small molecules on the basis of this example is used as Control Group 2.

[0074] Example 3

[0075] This example provides a preparation method of a molybdenum sulfide-based catalyst. The difference from Example 1 is that cobalt sulfate is used instead of nickel nitrate, and organic small molecule C is used to replace organic small molecule A. (NH4)2MoO4, cobalt sulfate, organic small molecule C, and thiourea are mixed in a molar ratio of 1:0.1:0.3:2.5 to obtain a Co-MoS2 catalyst.

[0076] Among them, the synthesis method of organic small molecule C is the same as that of organic small molecule A in Example 1. The structural formula of organic small molecule C is as follows:

[0077]

[0078] The molybdenum sulfide-based catalyst obtained without adding organic small molecules on the basis of this example is used as Control Group 3.

[0079] Example 4

[0080] This example provides a preparation method of a molybdenum sulfide-based catalyst. The difference from Example 1 is that H2PtCl6·(H2O)6 is used instead of nickel nitrate, and organic small molecule D is used to replace organic small molecule A. (NH4)2MoO4, H2PtCl6·(H2O)6, organic small molecule D, and thiourea are mixed in a molar ratio of 1:0.2:0.5:2 to obtain a Pt-MoS2 catalyst.

[0081] Among them, the synthesis method of organic small molecule D is the same as that of organic small molecule A in Example 1, and the structural formula of organic small molecule D is as follows:

[0082]

[0083] On the basis of this example, the molybdenum sulfide-based catalyst obtained without adding organic small molecules is used as Control Group 4.

[0084] Example 5

[0085] This example provides a preparation method of a molybdenum sulfide-based catalyst. The difference from Example 1 is that Na2MoO4 is used instead of (NH4)2MoO4, RuCl3·3H2O is used instead of nickel nitrate, and organic small molecule E is used instead of organic small molecule A. Na2MoO4, RuCl3·3H2O, organic small molecule E and thiourea are mixed according to a molar ratio of 1:0.05:0.5:4 to obtain a Ru-MoS2 catalyst.

[0086] Among them, the synthesis method of organic small molecule E is the same as that of organic small molecule A in Example 1, and the structural formula of organic small molecule E is as follows:

[0087]

[0088] On the basis of this example, the molybdenum sulfide-based catalyst obtained without adding organic small molecules is used as Control Group 5.

[0089] Example 6

[0090] This example provides a preparation method of a molybdenum sulfide-based catalyst, including the following steps:

[0091] (NH4)2MoO4, organic small molecule A (the same as in Example 1) and thiourea are mixed according to a molar ratio of 1:0.5:2.5, and water is added to make a mixed solution; carbon nanotubes are added to the mixed solution, and the mass ratio of carbon nanotubes to (NH4)2MoO4 is 1:6, and ultrasonic dispersion is carried out evenly; then hydrothermal reaction is carried out at 220 °C for 15 h to obtain a carbon nanotube-supported MoS2-CNT-Z catalyst.

[0092] On the basis of this example, the molybdenum sulfide-based catalyst obtained without adding organic small molecules is used as Control Group 6.

[0093] Example 7

[0094] This example provides a preparation method of a molybdenum sulfide-based catalyst. The difference from Example 1 is that nickel nitrate is not added.

[0095] Comparative Example 1

[0096] This comparative example provides a method for preparing molybdenum disulfide, which is different from Example 7 in that succinic acid and dimethylformamide with a molar ratio of 1:1 are used to replace organic small molecule A, and the total molar amount of succinic acid and dimethylformamide is the same as that of organic small molecule A.

[0097] Test Example

[0098] This test example provides performance tests on the catalysts of each example, control group, and comparative example, which are specifically as follows:

[0099] The three-electrode test method is adopted. Using 1M KOH as the electrolyte, a mercury / mercuric oxide electrode as the reference electrode, and a graphite electrode as the counter electrode. The working electrode is based on nickel foam, and the catalyst to be tested is sprayed on the surface of the nickel foam, and the catalyst loading is 2mg / cm 2 。

[0100] Figure 5 are the linear sweep voltammetry (LSV) curves of the molybdenum disulfide catalysts of Example 1 and Control Group 1; among them, Ni-MoS2-Z is Example 1, and Ni-MoS2 is Control Group 1. Figure 6 are the LSV curves of the molybdenum disulfide catalysts of Example 2 and Control Group 2; among them, Fe-MoS2-Z is Example 2, and Fe-MoS2 is Control Group 2. Figure 7 are the LSV curves of the molybdenum disulfide catalysts of Example 3 and Control Group 3; among them, Co-MoS2-Z is Example 3, and Co-MoS2 is Control Group 3. Figure 8 are the LSV curves of the molybdenum disulfide catalysts of Example 4 and Control Group 4; among them, Pt-MoS2-Z is Example 4, and Pt-MoS2 is Control Group 4. Figure 9 are the LSV curves of the molybdenum disulfide catalysts of Example 5 and Control Group 5; among them, Ru-MoS2-Z is Example 5, and Ru-MoS2 is Control Group 5. Figure 10 are the LSV curves of the molybdenum disulfide catalysts of Example 6 and Control Group 6; among them, MoS2-CNT-Z is Example 6, and MoS2-CNT is Control Group 6. Figure 11 are the LSV curves of the molybdenum disulfide catalysts of Example 7 and Comparative Example 1; among them, MoS2-Z is Example 7, and MoS2-B is Comparative Example 1.

[0101] From Figures 5-9It can be seen that, compared with the control group, after the surface of the molybdenum sulfide-based catalyst of the present invention is modified with organic small molecules, the overpotential can be lower, the current density can be higher, and the gas production can be increased, indicating that the hydrogen evolution performance of the catalyst is better. Example 6 shows that when a carrier, such as carbon nanotubes, is added to the molybdenum sulfide catalyst, the organic small molecules can still improve the hydrogen evolution performance of the supported catalyst. Examples 7 and Comparative Example 1 show that the improvement of the hydrogen evolution performance of the molybdenum sulfide catalyst by the modification of organic small molecules not only comes from the phase transition and hydrophilic-hydrophobicity of MoS2, but the quaternary ammonium cations in the organic small molecules are the key to improving the hydrogen evolution performance on the surface of the molybdenum sulfide catalyst. This conclusion can be further verified by adding succinic acid and dimethylformamide in Comparative Example 1. Combining all the examples, the control group and Comparative Example 1 shows that the organic small molecules with quaternary ammonium cations have universality in improving the hydrogen evolution performance of the molybdenum sulfide-based catalyst, including pure molybdenum sulfide, doped molybdenum sulfide and supported molybdenum sulfide catalysts.

[0102] Obviously, the above examples are merely illustrations for clear explanation and are not limitations on the implementation manners. For those of ordinary skill in the art, other different forms of changes or modifications can be made based on the above description. It is not necessary and impossible to enumerate all the implementation manners here. And the obvious changes or modifications derived therefrom are still within the protection scope of the present invention.

Claims

1. An organic small molecule for improving the hydrogen evolution performance of molybdenum sulfide-based catalysts, characterized in that, The end groups at both ends of the organic small molecule respectively include a cation and an anion; the anion includes at least one of carboxylate ions, sulfonate ions, and phosphate ions; the cation has at least one of the following structural formulas:

2. The organic small molecule according to claim 1, wherein The organic small molecule has one of the following structural formulas: Wherein, n is 1-12.

3. The organic small molecule according to claim 2, wherein The organic small molecule has one of the following structural formulas: The n is 1-5.

4. A molybdenum sulfide-based catalyst, characterized in that, The molybdenum sulfide-based catalyst includes molybdenum sulfide, and the molybdenum sulfide includes a 1T phase; the molybdenum sulfide-based catalyst includes a quaternary ammonium group and also includes at least one of a carboxyl group, a sulfonic acid group, and a phosphoric acid group.

5. The molybdenum sulfide-based catalyst according to claim 4, wherein, The molybdenum sulfide-based catalyst includes a doped metal, and the doped metal includes a transition metal and / or a noble metal; and / or, The molybdenum sulfide-based catalyst further includes a carrier.

6. The molybdenum sulfide-based catalyst according to claim 5, wherein The doped metal includes at least one of nickel, iron, cobalt, platinum, and ruthenium; and / or, The carrier includes carbon nanotubes, graphene, or carbon fibers.

7. A preparation method of a molybdenum sulfide-based catalyst, characterized in that, Include a molybdenum source and an organic small molecule, and then carry out a hydrothermal reaction; the end groups at both ends of the organic small molecule respectively include a cation and an anion, the anion includes at least one of carboxylate ions, sulfonate ions, and phosphate ions, and the cation has at least one of the following structural formulas:

8. The preparation method according to claim 7, characterized in that, When carrying out the mixing, a sulfur source and / or a doped metal source are further included; and / or, When carrying out the mixing, a carrier is further included, and the carrier includes carbon nanotubes, graphene, or carbon fibers; preferably, the mass ratio of the carrier to the molybdenum source is 1:(6-10); and / or, The temperature of the hydrothermal reaction is 170-220 °C, and the time is 6-20 h; and / or, The organic small molecule has one of the following structural formulas: Wherein, n is 1-12.

9. The preparation method according to claim 7 or 8, characterized in that, The molybdenum source includes molybdate and / or paramolybdate; preferably, the paramolybdate includes (NH4)6Mo7O 24 ; the molybdate includes at least one of (NH4)2MoO4, Na2MoO4, and K2MoO4; and / or, The sulfur source includes a sulfur-containing compound, preferably, the sulfur-containing compound includes at least one of thiourea, thioether, and thioacetamide; and / or, The metal in the doped metal source includes at least one of nickel, iron, cobalt, platinum, and ruthenium; and / or, The doped metal source is a water-soluble salt of the doped metal; and / or, The molar ratio of the molybdenum element in the molybdenum source, the doped metal in the doped metal source, the organic small molecule, and the sulfur source is 1:(0.05-0.2):(0.1-0.5):(2-4); and / or, The molar ratio of the molybdenum element in the molybdenum source, the organic small molecule, and the sulfur source is 1:(0.1-0.5):(2-4).

10. Use of the molybdenum sulfide-based catalyst according to any one of claims 4-6 or the molybdenum sulfide-based catalyst according to any one of claims 7-9 in electrolytic water hydrogen evolution.

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