阅读说明：本技术 一种多相硫化钼复合材料及其制备方法和应用 (Multiphase molybdenum sulfide composite material and preparation method and application thereof ) 是由 欧阳柳章 陈沛荣 王辉 朱敏 于 2021-08-12 设计创作，主要内容包括：本发明公开了一种多相硫化钼复合材料及其制备方法和应用。本发明的多相硫化钼复合材料的组成包括MoS-(2)和Mo-(2)S-(3),还可以包括Mo-(3)S-(4)。本发明的多相硫化钼复合材料的制备方法包括以下步骤：将氯化钼、镁粉和硫粉混合,进行固相球磨、酸洗和干燥,即得多相硫化钼复合材料。本发明的多相硫化钼复合材料用作电催化析氢反应的催化剂具有很好的催化活性,且其制备方法简单、能耗低、成本低,适合大规模生产应用。(The invention discloses a multiphase molybdenum sulfide composite material and a preparation method and application thereof. The composition of the multiphase molybdenum sulfide composite material comprises MoS 2 And Mo 2 S 3 May also comprise Mo 3 S 4 . The preparation method of the multiphase molybdenum sulfide composite material comprises the following steps: mixing molybdenum chloride, magnesium powder and sulfur powder, and carrying out solid-phase ball milling, acid washing and drying to obtain the multiphase molybdenum sulfide composite material. The heterogeneous molybdenum sulfide composite material has good catalytic activity when used as a catalyst for electrocatalytic hydrogen evolution reaction, and the preparation method is simple, low in energy consumption and low in cost, and is suitable for large-scale production and application.)

1. A multiphase molybdenum sulfide composite material is characterized by comprising MoS₂And Mo₂S₃。

2. The multiphase molybdenum sulfide composite of claim 1, wherein: the composition of the multiphase molybdenum sulfide composite material also comprises Mo₃S₄。

3. A method of preparing a multiphase molybdenum sulphide composite material according to claim 1 or 2, comprising the steps of: mixing molybdenum chloride, magnesium powder and sulfur powder, and carrying out solid-phase ball milling, acid washing and drying to obtain the multiphase molybdenum sulfide composite material.

4. The method of preparing a multiphase molybdenum sulfide composite material according to claim 3, wherein: the molar ratio of the molybdenum chloride to the magnesium powder to the sulfur powder is 1: 3-4: 4-8.

5. The method of preparing a multiphase molybdenum sulfide composite material according to claim 3 or 4, wherein: the solid phase ball milling is carried out in a protective atmosphere.

6. The method of preparing a multiphase molybdenum sulfide composite material according to claim 3 or 4, wherein: the solid-phase ball milling is carried out under the condition that the rotating speed of the ball mill is 400 rpm-500 rpm, and the ball milling time is 8 h-20 h.

7. The method of preparing a multiphase molybdenum sulfide composite material according to claim 3 or 4, wherein: the ball-material ratio of the solid-phase ball milling is 20: 1-100: 1.

8. The method of preparing a multiphase molybdenum sulfide composite material according to claim 3 or 4, wherein: the acid adopted by the acid cleaning is one of hydrochloric acid, sulfuric acid and phosphoric acid.

9. The method of preparing a multiphase molybdenum sulfide composite material according to claim 8, wherein: the concentration of the hydrochloric acid and the concentration of the sulfuric acid are both 1 mol/L-6 mol/L; the mass fraction of the phosphoric acid is 10-25%.

10. Use of the heterogeneous molybdenum sulphide composite material according to claim 1 or 2 for the preparation of a catalyst for the electrocatalytic hydrogen evolution reaction.

Technical Field

The invention relates to the technical field of molybdenum sulfide materials, in particular to a multiphase molybdenum sulfide composite material and a preparation method and application thereof.

Background

Molybdenum is a transition metal element, and sulfides (such as molybdenum disulfide, molybdenum trisulfide and the like) of molybdenum have wide application in solid lubrication, semiconductor materials, energy storage devices, energy conversion devices, catalytic materials and the like. The molybdenum disulfide nanosheet has special boundary and size characteristics, is regarded as a material with the potential of replacing a noble metal Pt catalyst in the field of electrocatalytic hydrogen evolution, but has poor conductivity and is not beneficial to charge transmission. Molybdenum trisulfide can exhibit more metallic properties and better conductivity than molybdenum disulfide, and has received much attention in recent years.

Molybdenum disulfide is typically produced by a hydrothermal or vapor phase process, for example: kim et al in MoCl₅And S is used as a raw material, and molybdenum disulfide nanosheets (Journal of Physics and Chemistry of Solids 2015, 87, 32-37) are obtained by a chemical vapor deposition method at high temperature in a protective atmosphere. Molybdenum trisulfide is generally obtained by heat treatment of molybdenum disulfide (heat treatment of molybdenum disulfide to remove S atoms from its surface and further obtain Mo₂S₃) To obtain, for example: kozlova et al by ultra-high temperature at 1150 ℃ on MoS₂Carrying out heat treatment to finally obtain Mo with a lamellar structure₂S₃Material (j.mater.chem.c,2017,5, 6601-6610); zhou et al synthesized Mo with sea urchin-like morphology by salt melting assisted method₂S₃Material (chem. commun.,2018,54, 12714). The above examples are typical examples of preparing molybdenum disulfide or molybdenum trisulfide, and all have the problems of low yield, high temperature and high energy cost.

Disclosure of Invention

The invention aims to provide a multiphase molybdenum sulfide composite material, and a preparation method and application thereof.

The technical scheme adopted by the invention is as follows:

a multi-phase molybdenum sulfide composite material comprises MoS₂And Mo₂S₃May also comprise Mo₃S₄。

The preparation method of the multiphase molybdenum sulfide composite material comprises the following steps: mixing molybdenum chloride, magnesium powder and sulfur powder, and carrying out solid-phase ball milling, acid washing and drying to obtain the multiphase molybdenum sulfide composite material.

Preferably, the molar ratio of the molybdenum chloride to the magnesium powder to the sulfur powder is 1: 3-4: 4-8.

Preferably, the solid phase ball milling is performed in a protective atmosphere.

Preferably, the protective atmosphere is an argon atmosphere.

Preferably, the solid phase ball milling is performed at room temperature (15 ℃ C. to 35 ℃ C.).

Preferably, the solid-phase ball milling is carried out at the rotation speed of 400 rpm-500 rpm of the ball mill, and the ball milling time is 8 h-20 h.

Preferably, the ball-to-material ratio of the solid-phase ball milling is 20: 1-100: 1.

Preferably, the acid used for acid washing is one of hydrochloric acid, sulfuric acid and phosphoric acid.

Preferably, the concentration of the hydrochloric acid is 1mol/L to 6 mol/L.

Preferably, the concentration of the sulfuric acid is 1mol/L to 6 mol/L.

Preferably, the mass fraction of the phosphoric acid is 10% to 25%.

The invention has the beneficial effects that: the composition of the multiphase molybdenum sulfide composite material comprises MoS₂And Mo₂S₃May also comprise Mo₃S₄The catalyst has good catalytic activity when being used as a catalyst for electrocatalytic hydrogen evolution reaction, and the preparation method is simple, low in energy consumption and cost and suitable for large-scale production and application.

Specifically, the method comprises the following steps:

1) MoS in the multiphase molybdenum sulfide composite material of the invention₂And Mo₂S₃The catalyst has a synergistic effect, improves the overall catalytic activity of the material, and has good catalytic activity when being used as a catalyst for electrocatalytic hydrogen evolution reaction;

2) the preparation process of the multiphase molybdenum sulfide composite material is simple, high-temperature heat treatment is not needed, an additional heat source is not needed to be introduced in the whole process, the energy consumption is low, and the cost is low.

Drawings

Figure 1 is an XRD pattern of the multiphase molybdenum sulfide composite of example 1.

FIG. 2 is an SEM image of the multiphase molybdenum sulfide composite of example 1.

Fig. 3 is an LSV plot of electrochemical hydrogen evolution under acidic conditions for the multiphase molybdenum sulfide composite of example 1.

Figure 4 is an XRD pattern of the multiphase molybdenum sulfide composite of example 7.

FIG. 5 is an SEM image of a multiphase molybdenum sulfide composite of example 7.

Fig. 6 is an LSV plot of electrochemical hydrogen evolution under acidic conditions for the multiphase molybdenum sulfide composite of example 7.

Detailed Description

The invention will be further explained and illustrated with reference to specific examples.

Example 1:

a preparation method of the multiphase molybdenum sulfide composite material comprises the following steps:

filling argon into a glove box until the pressure in the glove box is 0.1MPa, mixing molybdenum chloride, magnesium powder and sulfur powder in the glove box according to the molar ratio of 1:3:4, filling the mixture into a ball milling tank, adding a ball milling medium according to the ball material ratio of 100:1, adding the ball milling tank into a planetary ball mill, adjusting the rotating speed of the ball mill to 500 r/min, carrying out ball milling for 8h in argon atmosphere, adding a ball milling product into a hydrochloric acid solution with the concentration of 1mol/L, stirring, centrifuging, washing the centrifuged solid to be neutral, and drying in a drying box overnight to obtain the multiphase molybdenum sulfide composite material.

And (3) performance testing:

1) the X-ray diffraction (XRD) pattern of the multi-phase molybdenum sulfide composite material of this example is shown in fig. 1.

As can be seen from fig. 1: MoS can be observed₂Phase and Mo₂S₃The phase, i.e., the multiphase molybdenum sulfide composite of this example, was made of MoS₂And Mo₂S₃And (4) forming.

2) A Scanning Electron Microscope (SEM) image of the multiphase molybdenum sulfide composite material of the present example is shown in fig. 2.

As can be seen from fig. 2: the multiphase molybdenum sulfide composite material is an agglomerated structure formed by molybdenum sulfide nanosheet layers, and the lamellar structure conforms to the structural characteristics of molybdenum disulfide.

3) The LSV curve of the electrochemical hydrogen evolution of the multiphase molybdenum sulfide composite material of the embodiment under the acidic condition (0.5mol/L sulfuric acid solution) is shown in FIG. 3 (the multiphase molybdenum sulfide composite material is loaded on a glassy carbon electrode, and the scanning speed is 5 mV/s).

As can be seen from fig. 3: the heterogeneous molybdenum sulfide composite of the present example exhibited excellent catalytic performance.

Example 2:

a preparation method of the multiphase molybdenum sulfide composite material comprises the following steps:

filling argon into a glove box until the pressure in the glove box is 0.1MPa, mixing molybdenum chloride, magnesium powder and sulfur powder in the glove box according to the molar ratio of 1:3:5, filling the mixture into a ball milling tank, adding a ball milling medium according to the ball material ratio of 100:1, adding the ball milling tank into a planetary ball mill, adjusting the rotating speed of the ball mill to 500 r/min, carrying out ball milling for 8h in argon atmosphere, adding a ball milling product into a hydrochloric acid solution with the concentration of 1mol/L, stirring, centrifuging, washing the centrifuged solid to be neutral, and drying in a drying box overnight to obtain the multiphase molybdenum sulfide composite material.

The multiphase molybdenum sulfide composite material of the embodiment is tested to be composed of MoS₂And Mo₂S₃The composition, the micro-morphology and the catalytic performance of the composite material are very close to those of the multi-phase molybdenum sulfide composite material in the embodiment 1.

Example 3:

a preparation method of the multiphase molybdenum sulfide composite material comprises the following steps:

filling argon into a glove box until the pressure in the glove box is 0.1MPa, mixing molybdenum chloride, magnesium powder and sulfur powder in the glove box according to the molar ratio of 1:3:6, filling the mixture into a ball milling tank, adding a ball milling medium according to the ball material ratio of 100:1, adding the ball milling tank into a planetary ball mill, adjusting the rotating speed of the ball mill to 500 r/min, carrying out ball milling for 8h in argon atmosphere, adding a ball milling product into a hydrochloric acid solution with the concentration of 1mol/L, stirring, centrifuging, washing the centrifuged solid to be neutral, and drying in a drying box overnight to obtain the multiphase molybdenum sulfide composite material.

The multiphase molybdenum sulfide composite material of the embodiment is tested to be composed of MoS₂And Mo₂S₃The composition, the micro-morphology and the catalytic performance of the composite material are very close to those of the multi-phase molybdenum sulfide composite material in the embodiment 1.

Example 4:

a preparation method of the multiphase molybdenum sulfide composite material comprises the following steps:

filling argon into a glove box until the pressure in the glove box is 0.1MPa, mixing molybdenum chloride, magnesium powder and sulfur powder in the glove box according to the molar ratio of 1:3:4, filling the mixture into a ball milling tank, adding a ball milling medium according to the ball material ratio of 20:1, adding the ball milling tank into a planetary ball mill, adjusting the rotating speed of the ball mill to 400 r/min, carrying out ball milling in an argon atmosphere for 20h, adding a ball milling product into a hydrochloric acid solution with the concentration of 1mol/L, stirring, centrifuging, washing the centrifuged solid to be neutral, and drying in a drying box overnight to obtain the multiphase molybdenum sulfide composite material.

The multiphase molybdenum sulfide composite material of the embodiment is tested to be composed of MoS₂And Mo₂S₃The composition, the micro-morphology and the catalytic performance of the composite material are very close to those of the multi-phase molybdenum sulfide composite material in the embodiment 1.

Example 5:

a preparation method of the multiphase molybdenum sulfide composite material comprises the following steps:

filling argon into a glove box until the pressure in the glove box is 0.1MPa, mixing molybdenum chloride, magnesium powder and sulfur powder in the glove box according to the molar ratio of 1:3:5, filling the mixture into a ball milling tank, adding a ball milling medium according to the ball material ratio of 20:1, adding the ball milling tank into a planetary ball mill, adjusting the rotating speed of the ball mill to 400 r/min, carrying out ball milling in an argon atmosphere for 20h, adding a ball milling product into a sulfuric acid solution with the concentration of 1mol/L, stirring, centrifuging, washing the centrifuged solid to be neutral, and drying in a drying box overnight to obtain the multiphase molybdenum sulfide composite material.

The multiphase molybdenum sulfide composite material of the embodiment is tested to be composed of MoS₂And Mo₂S₃Composition, microstructure and catalytic properties of the heterogeneous molybdenum sulfide composite of example 1Are very close.

Example 6:

a preparation method of the multiphase molybdenum sulfide composite material comprises the following steps:

filling argon into a glove box until the pressure in the glove box is 0.1MPa, mixing molybdenum chloride, magnesium powder and sulfur powder in the glove box according to the molar ratio of 1:3:6, filling the mixture into a ball milling tank, adding a ball milling medium according to the ball material ratio of 20:1, adding the ball milling tank into a planetary ball mill, adjusting the rotating speed of the ball mill to 400 r/min, carrying out ball milling in argon atmosphere for 20h, adding a ball milling product into a phosphoric acid solution with the mass fraction of 15%, stirring, centrifuging, washing the centrifuged solid to be neutral, and drying in a drying box overnight to obtain the multiphase molybdenum sulfide composite material.

The multiphase molybdenum sulfide composite material of the embodiment is tested to be composed of MoS₂And Mo₂S₃The composition, the micro-morphology and the catalytic performance of the composite material are very close to those of the multi-phase molybdenum sulfide composite material in the embodiment 1.

Example 7:

a preparation method of the multiphase molybdenum sulfide composite material comprises the following steps:

filling argon into a glove box until the pressure in the glove box is 0.1MPa, mixing molybdenum chloride, magnesium powder and sulfur powder in the glove box according to the molar ratio of 1:4:4, filling the mixture into a ball milling tank, adding a ball milling medium according to the ball material ratio of 20:1, adding the ball milling tank into a planetary ball mill, adjusting the rotating speed of the ball mill to 500 r/min, carrying out ball milling for 8h in argon atmosphere, adding a ball milling product into a hydrochloric acid solution with the concentration of 3mol/L, stirring, centrifuging, washing the centrifuged solid to be neutral, and drying in a drying box overnight to obtain the multiphase molybdenum sulfide composite material.

And (3) performance testing:

1) the XRD pattern of the multiphase molybdenum sulfide composite of this example is shown in fig. 4.

As can be seen from fig. 4: MoS can be observed₂Phase, Mo₂S₃Phase and Mo₃S₄The phase, i.e., the multiphase molybdenum sulfide composite of this example, was made of MoS₂、Mo₂S₃And Mo₃S₄And (4) forming.

2) An SEM image of the multiphase molybdenum sulfide composite of the present example is shown in fig. 5.

As can be seen from fig. 5: the multiphase molybdenum sulfide composite material of the embodiment is formed by particles formed by sheet agglomeration, and the sheet layers are flocculent, so that the structural characteristics of molybdenum disulfide and multiphase molybdenum sulfide are met.

3) The LSV curve of the multi-phase molybdenum sulfide composite material under acidic conditions is shown in FIG. 6 (the test method is the same as that in example 1).

As can be seen from fig. 6: the heterogeneous molybdenum sulfide composite of the present example exhibited excellent catalytic performance.

Example 8:

a preparation method of the multiphase molybdenum sulfide composite material comprises the following steps:

filling argon into a glove box until the pressure in the glove box is 0.1MPa, mixing molybdenum chloride, magnesium powder and sulfur powder in the glove box according to the molar ratio of 1:4:5, filling the mixture into a ball milling tank, adding a ball milling medium according to the ball material ratio of 20:1, adding the ball milling tank into a planetary ball mill, adjusting the rotating speed of the ball mill to 500 r/min, carrying out ball milling for 8h in argon atmosphere, adding a ball milling product into a hydrochloric acid solution with the concentration of 3mol/L, stirring, centrifuging, washing the centrifuged solid to be neutral, and drying in a drying box overnight to obtain the multiphase molybdenum sulfide composite material.

The multiphase molybdenum sulfide composite material of the embodiment is tested to be composed of MoS₂、Mo₂S₃And Mo₃S₄The composition, the micro-morphology and the catalytic performance of the composite material are very close to those of the multi-phase molybdenum sulfide composite material in the example 7.

Example 9:

a preparation method of the multiphase molybdenum sulfide composite material comprises the following steps:

filling argon into a glove box until the pressure in the glove box is 0.1MPa, mixing molybdenum chloride, magnesium powder and sulfur powder in the glove box according to the molar ratio of 1:4:4, filling the mixture into a ball milling tank, adding a ball milling medium according to the ball material ratio of 100:1, adding the ball milling tank into a planetary ball mill, adjusting the rotating speed of the ball mill to 400 r/min, carrying out ball milling for 8h in argon atmosphere, adding a ball milling product into a sulfuric acid solution with the concentration of 3mol/L, stirring, centrifuging, washing the centrifuged solid to be neutral, and drying in a drying box overnight to obtain the multiphase molybdenum sulfide composite material.

The multiphase molybdenum sulfide composite material of the embodiment is tested to be composed of MoS₂、Mo₂S₃And Mo₃S₄The composition, the micro-morphology and the catalytic performance of the composite material are very close to those of the multi-phase molybdenum sulfide composite material in the example 7.

Example 10:

a preparation method of the multiphase molybdenum sulfide composite material comprises the following steps:

filling argon into a glove box until the pressure in the glove box is 0.1MPa, mixing molybdenum chloride, magnesium powder and sulfur powder in the glove box according to the molar ratio of 1:4:6, filling the mixture into a ball milling tank, adding a ball milling medium according to the ball material ratio of 100:1, adding the ball milling tank into a planetary ball mill, adjusting the rotating speed of the ball mill to 400 r/min, carrying out ball milling for 20h in argon atmosphere, adding a ball milling product into a hydrochloric acid solution with the concentration of 6mol/L, stirring, centrifuging, washing the centrifuged solid to be neutral, and drying in a drying box overnight to obtain the multiphase molybdenum sulfide composite material.

The multiphase molybdenum sulfide composite material of the embodiment is tested to be composed of MoS₂、Mo₂S₃And Mo₃S₄The composition, the micro-morphology and the catalytic performance of the composite material are very close to those of the multi-phase molybdenum sulfide composite material in the example 7.

Example 11:

a preparation method of the multiphase molybdenum sulfide composite material comprises the following steps:

filling argon into a glove box until the pressure in the glove box is 0.1MPa, mixing molybdenum chloride, magnesium powder and sulfur powder in the glove box according to the molar ratio of 1:4:7, filling the mixture into a ball milling tank, adding a ball milling medium according to the ball material ratio of 100:1, adding the ball milling tank into a planetary ball mill, adjusting the rotating speed of the ball mill to 400 r/min, carrying out ball milling for 20h in argon atmosphere, adding a ball milling product into a hydrochloric acid solution with the concentration of 6mol/L, stirring, centrifuging, washing the centrifuged solid to be neutral, and drying in a drying box overnight to obtain the multiphase molybdenum sulfide composite material.

The multiphase molybdenum sulfide composite material of the embodiment is tested to be composed of MoS₂And Mo₂S₃The composition, the micro-morphology and the catalytic performance of the composite material are very close to those of the multi-phase molybdenum sulfide composite material in the embodiment 1.

Example 12:

a preparation method of the multiphase molybdenum sulfide composite material comprises the following steps:

filling argon into a glove box until the pressure in the glove box is 0.1MPa, mixing molybdenum chloride, magnesium powder and sulfur powder in the glove box according to the molar ratio of 1:4:8, filling the mixture into a ball milling tank, adding a ball milling medium according to the ball material ratio of 100:1, adding the ball milling tank into a planetary ball mill, adjusting the rotating speed of the ball mill to 400 r/min, carrying out ball milling for 20h in argon atmosphere, adding a ball milling product into a phosphoric acid solution with the mass fraction of 25%, stirring, centrifuging, washing the centrifuged solid to be neutral, and drying in a drying box overnight to obtain the multiphase molybdenum sulfide composite material.

The multiphase molybdenum sulfide composite material of the embodiment is tested to be composed of MoS₂And Mo₂S₃The composition, the micro-morphology and the catalytic performance of the composite material are very close to those of the multi-phase molybdenum sulfide composite material in the embodiment 1.

The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.