Preparation method of two-dimensional acetylene-rich carbon / molybdenum sulfide heterostructure hydrogen production catalyst

Abstract

The invention is applicable to the technical field of nano material preparation, and provides a preparation method of a two-dimensional acetylene-rich carbon / molybdenum sulfide heterostructure hydrogen production catalyst, which comprises the following steps: adding molybdenum sulfide into a solution to prepare a suspension A; adding soluble cuprous salt into the turbid liquid A in an inert atmosphere to obtain a mixed liquid B; alkynyl benzene is added into an organic solvent, and a mixed solution C is obtained; dropwise adding the mixed solution C into the mixed solution B under a continuous stirring condition, and reacting to obtain a mixed solution D; centrifuging the mixed solution D to obtain a precursor E; and cleaning the precursor E, and carrying out vacuum drying to obtain the two-dimensional acetylene-enriched carbon / molybdenum sulfide heterostructure hydrogen production catalyst. No additive is needed in the preparation process, and the product purity is high; by constructing a special two-dimensional heterostructure, the problem of molybdenum sulfide is solved, and the intrinsic activity and stability of the material are remarkably improved. The preparation method has the advantages of easily available raw materials, simple process, low cost and environmental protection, and is suitable for industrial production.

Description

Technical Field

[0001] The present invention belongs to the technical field of nanomaterial preparation, and particularly relates to a preparation method of a two-dimensional alkyne-rich carbon / molybdenum disulfide heterostructure hydrogen production catalyst. Background Art

[0002] Alkyne-rich carbon is a class of carbon allotropes with natural pore structures, and its network structure includes sp-hybridized alkyne-bonded carbon atoms. This special structure endows alkyne-rich carbon with excellent properties, such as a natural band gap, excellent conductivity and electron mobility, good mechanical properties and chemical stability, a unique pore structure, special electronic structure properties, semiconductor properties close to silicon, and excellent stability, making it have great application potential in the fields of catalysis, batteries, electronic devices, semiconductors, and energy storage.

[0003] As a typical two-dimensional layered material, molybdenum disulfide is regarded as a promising hydrogen production catalyst. However, its poor conductivity and limited exposed active sites limit its catalytic activity and practical applications.

[0004] At present, there is no research report on the method for preparing a hydrogen production catalyst by combining two-dimensional alkyne-rich carbon with molybdenum disulfide. Therefore, developing a preparation method of a two-dimensional alkyne-rich carbon / molybdenum disulfide heterostructure hydrogen production catalyst with simple process, green environmental protection, easy operation, conventional equipment, and easy industrial production is of great significance in the fields of catalysis, batteries, electronic devices, semiconductors, and energy storage. For this reason, the present invention proposes a preparation method of a two-dimensional alkyne-rich carbon / molybdenum disulfide heterostructure hydrogen production catalyst. Summary of the Invention

[0005] The purpose of the present invention is to provide a preparation method of a two-dimensional alkyne-rich carbon / molybdenum disulfide heterostructure hydrogen production catalyst, aiming to solve the problems raised in the above background art.

[0006] The purpose of the present invention is achieved through the following technical solutions: A preparation method of a two-dimensional alkyne-rich carbon / molybdenum disulfide heterostructure hydrogen production catalyst includes the following steps: Step 1: Add molybdenum disulfide to an organic solvent or a mixed solution of an organic solvent and water, and mix for 1 - 5 h by ultrasonic treatment to prepare a suspension A with a concentration of 0.1 - 5 mg / mL; Step 2: Add a soluble monovalent copper salt to the suspension A in an inert atmosphere, and stir for 20 - 60 min to obtain a mixed solution B with a concentration of cuprous ion of 0.01 - 0.5 mol / L; Step 3: Add alkynylbenzene to an organic solvent to obtain a mixed solution C; Step 4: Dropwise add the mixed solution C to the mixed solution B under continuous stirring, and react at 10 - 200 °C for 10 - 60 min to obtain a mixed solution D; Step 5: Centrifuge the mixture D at a speed of 8000 - 20000 revolutions per minute for 5 - 30 minutes to obtain the precursor E; Step 6: Wash the precursor E and vacuum dry it at 40 - 80 °C. After natural cooling to room temperature, a two-dimensional alkynyl-rich carbon / molybdenum sulfide heterostructure hydrogen production catalyst is obtained.

[0007] Furthermore, in the said Step 1, the organic solvent is at least one of dichloromethane, chloroform, N,N-dimethylformamide, acetone, toluene, pyridine, triethylamine, diethylamine, and absolute ethanol.

[0008] Furthermore, in the said Step 2, the inert atmosphere is an inert gas, and the inert gas is at least one of argon, nitrogen, and helium.

[0009] Furthermore, in the said Step 2, the soluble monovalent copper salt is at least one of cuprous iodide, cuprous bromide, and cuprous chloride.

[0010] Furthermore, in the said Step 3, the organic solvent is at least one of dichloromethane, chloroform, N,N-dimethylformamide, acetone, toluene, xylene, ethyl acetate, ether, pyridine, triethylamine, diethylamine, and absolute ethanol.

[0011] Furthermore, in the said Step 3, the concentration of ethynylbenzene in the mixture C is not less than 0.1 mg / mL.

[0012] Furthermore, in the said Step 6, the cleaning solution used to wash the precursor E is at least one of hydrochloric acid, sodium hydroxide, absolute ethanol, and acetone.

[0013] A two-dimensional alkynyl-rich carbon / molybdenum sulfide heterostructure hydrogen production catalyst prepared by the above-mentioned preparation method, wherein the two-dimensional alkynyl-rich carbon / molybdenum sulfide heterostructure hydrogen production catalyst is a molybdenum sulfide structure coated with alkynyl-rich carbon, with a size distribution of 10 - 500 nm and a thickness of 1 - 20 nm.

[0014] An application of the above-mentioned two-dimensional alkynyl-rich carbon / molybdenum sulfide heterostructure hydrogen production catalyst in catalytic hydrogen evolution.

[0015] Compared with the prior art, the beneficial effects of the present invention are: The hydrogen production catalyst of two-dimensional alkyne-rich carbon / molybdenum sulfide heterostructure prepared by the present invention has a unique structure, and no additives are required during the preparation process, and the product purity is high. Compared with single molybdenum sulfide, the composite of molybdenum sulfide and alkyne-rich carbon not only solves the problems of poor conductivity and limited active sites of molybdenum sulfide, but also significantly improves the intrinsic activity and stability of the material through a special two-dimensional heterostructure. The raw materials used in the present invention are easily available, the preparation method is ingeniously designed, the process is simple, rapid, easy to operate, low in cost, the equipment is conventional, green and environmentally friendly, and it is suitable for industrial production. Description of the Drawings

[0016] Figure 1 It is an X-ray diffraction (XRD) pattern of the hydrogen production catalyst of two-dimensional alkyne-rich carbon / molybdenum sulfide heterostructure prepared in Example 1.

[0017] Figure 2 It is an X-ray photoelectron spectroscopy (XPS) pattern of the hydrogen production catalyst of two-dimensional alkyne-rich carbon / molybdenum sulfide heterostructure prepared in Example 1.

[0018] Figure 3 It is a transmission electron microscopy (TEM) pattern of the hydrogen production catalyst of two-dimensional alkyne-rich carbon / molybdenum sulfide heterostructure prepared in Example 1.

[0019] Figure 4 It is a test result graph of hydrogen production by electrolyzing water of the hydrogen production catalyst of two-dimensional alkyne-rich carbon / molybdenum sulfide heterostructure prepared in Example 1 in 1.0 M KOH electrolyte; wherein a is the linear polarization curve of MoS2 / C, MoS2, Pt / C and C in 1.0 M KOH electrolyte; b is the Tafel slope curve of MoS2 / C, MoS2, Pt / C and C; c is the current-time curve graph of the catalyst MoS2 / C. Detailed Description of the Invention

[0020] In order to have a clearer understanding of the technical features, objectives and beneficial effects of the present invention, the technical solutions of the present invention are described in detail below, but it should not be construed as a limitation on the scope of implementation of the present invention.

[0021] The present invention provides a preparation method of a hydrogen production catalyst of two-dimensional alkyne-rich carbon / molybdenum sulfide heterostructure, and the method includes the following steps: Step 1: Add 0.01-2 g of molybdenum sulfide to 10-1000 mL of an organic solvent or a mixed solution of 10-1000 mL of an organic solvent and water, and mix for 1-5 h by ultrasonic treatment to prepare a suspension A with a concentration of 0.1-5 mg / mL. The organic solvent is at least one of dichloromethane, chloroform, N,N-dimethylformamide, acetone, toluene, pyridine, triethylamine, diethylamine and absolute ethanol.

[0022] Step 2: Add 0.001 - 10 g of soluble monovalent copper salt into suspension A under an inert atmosphere, stir for 20 - 60 min to obtain a mixed solution B with a concentration of cuprous ion of 0.01 - 1.5 mol / L. The inert atmosphere is an inert gas, and the inert gas is at least one of argon, nitrogen, and helium. The soluble monovalent copper salt is at least one of cuprous iodide, cuprous bromide, and cuprous chloride.

[0023] Step 3: Add 0.1 - 600 mg of ethynylbenzene to 10 - 1000 mL of an organic solvent to obtain a mixed solution C. The organic solvent is at least one of dichloromethane, chloroform, N,N - dimethylformamide, acetone, toluene, xylene, ethyl acetate, ether, pyridine, triethylamine, diethylamine, and absolute ethanol. The concentration of ethynylbenzene in the mixed solution C is not less than 0.1 mg / mL.

[0024] Step 4: Dropwise add the mixed solution C into the mixed solution B under continuous stirring, and react at 10 - 200 °C for 10 - 60 min to obtain a mixed solution D; Step 5: Centrifuge the mixed solution D at a speed of 8000 - 20000 revolutions per minute for 5 - 30 min to obtain a precursor E; Step 6: Wash the precursor E, and vacuum - dry it at 40 - 80 °C for 1 - 10 h. After naturally cooling to room temperature, a two - dimensional ethynyl - rich carbon / molybdenum sulfide heterostructure hydrogen - production catalyst is obtained. The cleaning solution used to wash the precursor E is at least one of hydrochloric acid, sodium hydroxide, absolute ethanol, and acetone.

[0025] The present invention provides a two - dimensional ethynyl - rich carbon / molybdenum sulfide heterostructure hydrogen - production catalyst prepared by the above - mentioned preparation method. The two - dimensional ethynyl - rich carbon / molybdenum sulfide heterostructure hydrogen - production catalyst is a molybdenum sulfide structure coated with ethynyl - rich carbon, with a size distribution of 10 - 500 nm and a thickness of 1 - 20 nm.

[0026] The present invention provides an application of the above - mentioned two - dimensional ethynyl - rich carbon / molybdenum sulfide heterostructure hydrogen - production catalyst in catalytic hydrogen evolution.

[0027] The following describes the specific implementation of the present invention in detail with specific examples.

[0028] Example 1: This example provides a preparation method of a two - dimensional ethynyl - rich carbon / molybdenum sulfide heterostructure hydrogen - production catalyst. The specific steps are as follows: Step 1: Add 20 mg of molybdenum sulfide to 40 mL of pyridine, and ultrasonicate for 1 h to prepare a suspension A with a concentration of 0.5 mg / mL; Step 2: Under the protection of argon (Ar), add 761.8 mg of soluble cuprous iodide into the suspension A, stir for 20 min to obtain a mixed solution B with a concentration of cuprous ion of 0.1 mol / L; Step 3: Add 10 mg of ethynylbenzene to 20 mL of pyridine to obtain a mixed solution C with a concentration of 0.5 mg / mL; Step 4: Dropwise add the mixed solution C into the mixed solution B under continuous stirring, and react at 60 °C for 30 min to obtain a mixed solution D; Step 5: Centrifuge the mixed solution D at a speed of 10,000 rpm for 20 min to obtain a precursor E; Step 6: Wash the precursor E with absolute ethanol, vacuum dry it at 70 °C for 2 h, and after natural cooling to room temperature, obtain a two-dimensional ethynyl-rich carbon / molybdenum disulfide heterostructure hydrogen production catalyst (MoS2 / C catalyst).

[0029] To characterize the MoS2 / C catalyst prepared in Example 1, X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), and transmission electron microscopy (TEM) analyses were carried out, and the results are shown in Figure 1 、 Figure 2 and Figure 3 respectively. It can be seen from Figure 1 that the preparation of the MoS2 / C catalyst was successfully achieved. It can be seen from Figure 2 the distribution of Mo, S, and C elements in the MoS2 / C catalyst sample. It can be seen from Figure 3 the typical lattice fringes of the MoS2 / C catalyst. Through the results of these characterization methods, it can be proved that the prepared MoS2 / C catalyst has an ideal structure and composition, providing a structural basis for its excellent hydrogen production performance.

[0030] Furthermore, the hydrogen production performance of the MoS2 / C catalyst prepared in Example 1 in 1.0 M KOH electrolyte was studied, and the results are shown in Figure 4 a-c. It can be seen from Figure 4 a that at the same applied potential, the MoS2 / C catalyst has a larger current density than commercial Pt / C, indicating its more excellent hydrogen production performance. It can be seen from Figure 4 b that the Tafel slope value of the MoS2 / C catalyst is smaller than that of commercial Pt / C, proving its faster kinetic properties and better catalytic activity. It can be seen from Figure 4 c that after at least 42 h of continuous hydrogen production test, the activity of the MoS2 / C catalyst hardly decreases, indicating its excellent stability.

[0031] In summary, a two-dimensional ethynyl-rich carbon / molybdenum disulfide heterostructure hydrogen production catalyst was successfully prepared in Example 1, and this catalyst exhibits excellent performance in electrolytic water hydrogen production.

[0032] Example 2: This example provides a method for preparing a two-dimensional alkynyl-rich carbon / molybdenum disulfide heterostructure hydrogen production catalyst. The specific steps are as follows: Step 1: Add 0.3 g of molybdenum disulfide to 200 mL of pyridine and ultrasonicate for 1 h to prepare suspension A with a concentration of 1.5 mg / mL. Step 2: Under the protection of argon (Ar), add 5.38 g of soluble cuprous chloride to suspension A and stir for 30 min to obtain mixture B with a cuprous ion concentration of 0.2 mol / L. Step 3: Add 30 mg of ethynylbenzene to 20 mL of pyridine to obtain mixture C with a concentration of 1.5 mg / mL. Step 4: Dropwise add mixture C to mixture B under continuous stirring, and react at 60 °C for 30 min to obtain mixture D. Step 5: Centrifuge mixture D at a speed of 10,000 rpm for 20 min to obtain precursor E. Step 6: Wash precursor E with absolute ethanol, vacuum dry at 70 °C for 2 h, and naturally cool to room temperature to obtain a two-dimensional alkynyl-rich carbon / molybdenum disulfide heterostructure hydrogen production catalyst (MoS2 / C catalyst).

[0033] Example 3: This example provides a method for preparing a two-dimensional alkynyl-rich carbon / molybdenum disulfide heterostructure hydrogen production catalyst. The specific steps are as follows: Step 1: Add 20 mg of molybdenum disulfide to 10 mL of acetone and ultrasonicate for 2 h to prepare suspension A with a concentration of 2.0 mg / mL. Step 2: Under the protection of argon (Ar), add 3.81 g of cuprous iodide to suspension A and stir for 30 min to obtain mixture B with a cuprous ion concentration of 1 mol / L. Step 3: Add 20 mg of ethynylbenzene to 10 mL of acetone to obtain mixture C with a concentration of 2 mg / mL. Step 4: Dropwise add mixture C to mixture B under continuous stirring, and react at 60 °C for 30 min to obtain mixture D. Step 5: Centrifuge mixture D at a speed of 10,000 rpm for 20 min to obtain precursor E. Step 6: Wash precursor E with absolute ethanol, vacuum dry at 70 °C for 2 h, and naturally cool to room temperature to obtain a two-dimensional alkynyl-rich carbon / molybdenum disulfide heterostructure hydrogen production catalyst (MoS2 / C catalyst).

[0034] Example 4: This example provides a method for preparing a two-dimensional alkynyl-rich carbon / molybdenum disulfide heterostructure hydrogen production catalyst. The specific steps are as follows: Step 1: Add 20 mg of molybdenum sulfide to 40 mL of pyridine, and ultrasonicate for 2 h to prepare suspension A with a concentration of 0.5 mg / mL. Step 2: Under the protection of argon (Ar), add 6.09 g of cuprous iodide to suspension A and stir for 50 min to obtain mixture B with a concentration of cuprous ions of 0.8 mol / L. Step 3: Add 20 mg of ethynylbenzene to 4 mL of acetone to obtain mixture C with a concentration of 5 mg / mL. Step 4: Dropwise add mixture C to mixture B under continuous stirring, and react at 70 °C for 30 min to obtain mixture D. Step 5: Centrifuge mixture D at a speed of 10,000 r / min for 20 min to obtain precursor E. Step 6: Wash precursor E with absolute ethanol, vacuum dry at 70 °C for 2 h, and naturally cool to room temperature to obtain a two-dimensional ethynyl-rich carbon / molybdenum sulfide heterostructure hydrogen production catalyst (MoS2 / C catalyst).

[0035] The above is only the preferred embodiment of the present invention. It should be noted that for those skilled in the art, without departing from the concept of the present invention, several modifications and improvements can be made, which should also be regarded as the protection scope of the present invention, and these will not affect the implementation effect of the present invention and the practicability of the patent.

Claims

1. A preparation method of a two-dimensional alkyne-rich carbon / molybdenum disulfide heterostructure hydrogen production catalyst, characterized in that, It includes the following steps: Step 1: Add molybdenum sulfide to an organic solvent or a mixed solution of an organic solvent and water, and mix them for 1 - 5 h by ultrasonic treatment to prepare a suspension A with a concentration of 0.1 - 5 mg / mL; Step 2: Add a soluble monovalent copper salt to the suspension A in an inert atmosphere, and stir for 20 - 60 min to obtain a mixed solution B with a concentration of cuprous ion of 0.01 - 0.5 mol / L; Step 3: Add ethynylbenzene to an organic solvent to obtain a mixed solution C; Step 4: Dropwise add the mixed solution C to the mixed solution B under continuous stirring, and react at 10 - 200 °C for 10 - 60 min to obtain a mixed solution D; Step 5: Centrifuge the mixed solution D at a speed of 8000 - 20000 revolutions per minute for 5 - 30 min to obtain a precursor E; Step 6: Wash the precursor E, and vacuum dry it at 40 - 80 °C. After naturally cooling to room temperature, a two-dimensional ethynyl-rich carbon / molybdenum sulfide heterostructure hydrogen production catalyst is obtained.

2. The preparation method according to claim 1, wherein In the said Step 1, the organic solvent is at least one of dichloromethane, chloroform, N,N-dimethylformamide, acetone, toluene, pyridine, triethylamine, diethylamine, and absolute ethanol.

3. The preparation method according to claim 1, characterized in that, In the said Step 2, the inert atmosphere is an inert gas, and the inert gas is at least one of argon, nitrogen, and helium.

4. The preparation method according to claim 1, characterized in that In the said Step 2, the soluble monovalent copper salt is at least one of cuprous iodide, cuprous bromide, and cuprous chloride.

5. The preparation method according to claim 1, characterized in that, In the said Step 3, the organic solvent is at least one of dichloromethane, chloroform, N,N-dimethylformamide, acetone, toluene, xylene, ethyl acetate, ether, pyridine, triethylamine, diethylamine, and absolute ethanol.

6. The preparation method according to claim 1, characterized in that, In the said Step 3, the concentration of ethynylbenzene in the mixed solution C is not less than 0.1 mg / mL.

7. The preparation method according to claim 1, characterized in that, In the said Step 6, the cleaning solution used to wash the precursor E is at least one of hydrochloric acid, sodium hydroxide, absolute ethanol, and acetone.

8. A two-dimensional rich-alkyne carbon / molybdenum sulfide heterostructure hydrogen production catalyst prepared by the preparation method according to any one of claims 1-7, characterized in that, The said two-dimensional ethynyl-rich carbon / molybdenum sulfide heterostructure hydrogen production catalyst is a structure of molybdenum sulfide coated with ethynyl-rich carbon, with a size distribution of 10 - 500 nm and a thickness of 1 - 20 nm.

9. Application of the two-dimensional ethynyl-rich carbon / molybdenum sulfide heterostructure hydrogen production catalyst according to claim 8 in catalytic hydrogen evolution.

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