CN108686710B - Two-dimensional metal organic framework/molybdenum disulfide nano composite electro-catalytic hydrogen evolution material and preparation method thereof - Google Patents

Two-dimensional metal organic framework/molybdenum disulfide nano composite electro-catalytic hydrogen evolution material and preparation method thereof Download PDF

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CN108686710B
CN108686710B CN201810461343.6A CN201810461343A CN108686710B CN 108686710 B CN108686710 B CN 108686710B CN 201810461343 A CN201810461343 A CN 201810461343A CN 108686710 B CN108686710 B CN 108686710B
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molybdenum disulfide
metal organic
organic framework
hydrogen evolution
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CN108686710A (en
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朱敏
马强
代娆
张静
刘戈
刘晨
郝兴彤
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Xijing University
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    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
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    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
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    • C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
    • C25B11/091—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of at least one catalytic element and at least one catalytic compound; consisting of two or more catalytic elements or catalytic compounds
    • C25B11/095—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of at least one catalytic element and at least one catalytic compound; consisting of two or more catalytic elements or catalytic compounds at least one of the compounds being organic
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    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis

Abstract

The invention provides a two-dimensional metal organic framework/molybdenum disulfide nano composite electro-catalytic hydrogen evolution material, which comprises two-dimensional metal organic framework nanosheets M-TCPP and molybdenum disulfide nanosheets MoS which are mutually dispersed2Wherein M is selected from Co2+、Ni2+Is 5,10,15, 20-tetrakis (4-carboxy-phenyl) -porphyrin, the molar ratio of M to Mo ions being 1: 0.4-8, the invention also provides a preparation method of the material; the preparation method can increase the hydrogen evolution reaction active sites on the surface of the material, and MoS2The conductivity of the two-dimensional metal organic framework/molybdenum disulfide nano composite electro-catalysis hydrogen evolution material is enhanced, the electro-catalysis hydrogen evolution performance of the two-dimensional metal organic framework/molybdenum disulfide nano composite electro-catalysis hydrogen evolution material is obviously improved, and a new method is provided for developing an electro-catalysis hydrogen evolution catalyst with low price and high efficiency.

Description

Two-dimensional metal organic framework/molybdenum disulfide nano composite electro-catalytic hydrogen evolution material and preparation method thereof
Technical Field
The invention relates to the technical field of electrocatalytic hydrogen evolution, in particular to a two-dimensional metal organic framework/molybdenum disulfide nano composite electrocatalytic hydrogen evolution material and a preparation method thereof.
Background
Along with the increasing energy crisis and environmental pollution problemsAt the same time, people's normal life and production have been seriously threatened. However, fossil energy sources (coal, oil and natural gas) have been the main sources of energy in the world, they are limited reserves of non-renewable energy and combustion products can severely pollute the environment. With the increase of the demand of fossil fuels and the reduction of the reserves of fossil fuels, people are more urgent to develop green and efficient renewable energy sources. The hydrogen energy is called the cleanest energy of the twenty-first century, and has wide application prospect due to a series of advantages, such as rich sources, high combustion heat value, only water generation after the hydrogen is combusted, and the like. The most common hydrogen production methods at present are water electrolysis hydrogen production and fossil fuel hydrogen production. However, fossil fuel is a non-renewable energy source, and although the method can produce a large amount of hydrogen, the application prospect is worried. Water is abundant in the earth, and hydrogen is produced by electrolyzing water, so that the hydrogen is inexhaustible. At present, electric energy can be directly produced in various modes, and the cost is low. Therefore, the method for producing hydrogen by electrolyzing water can be applied to large-scale production, and has the advantages of high hydrogen production efficiency, simple process and operation process, no environmental pollution and the like. Electrolyzed water can be divided into two half-cell reactions, namely, Hydrogen Evolution Reaction (HER) and Oxygen Evolution Reaction (OER). Both oxygen evolution reactions and hydrogen evolution reactions require the use of electrocatalysts to reduce the overpotential of the electrochemical reactions. Overpotential refers to the difference between the applied voltage and the thermodynamic reaction electromotive force in an electrochemical process. The greater the overpotential, the greater the applied voltage that needs to be applied, and the more power is consumed. It is therefore necessary to develop highly efficient hydrogen evolution catalysts which significantly reduce the hydrogen evolution overpotential. Currently, the platinum group noble metals are electrocatalysts with the highest hydrogen evolution efficiency, and can realize hydrogen evolution reaction at a voltage very close to the electromotive force of thermodynamic reaction. However, since precious metal resources are scarce and expensive, large-scale industrial production of hydrogen is impossible. Scientists have been working on developing a catalyst with abundant sources and high catalytic hydrogen evolution performance to replace the platinum group noble metal. Of these materials, two-dimensional (2D) Transition Metal Dichalcogenide (TMD) nanoplates have become an attractive HThe ER electrocatalyst type has good electrocatalytic hydrogen evolution performance. Molybdenum disulfide (MoS) as a typical layered TMD material2) Nanoplatelets have recently been widely used as HER catalysts, which show several thin S-Mo-S layers by weak van der waals interactions. Both theoretical and experimental studies show that MoS2Δ G ofH*Does approach thermal neutrality, resulting in MoS2May be an effective HER catalyst, which is of great interest because of its abundant resources and low cost. But the conductivity of the catalyst is poor, and the exposed hydrogen evolution reaction active sites are relatively few, so that the electrocatalytic hydrogen evolution performance of the catalyst is still to be greatly improved.
Disclosure of Invention
The invention aims to solve the problems in the prior art and provides a two-dimensional metal organic framework/molybdenum disulfide nano composite electrocatalytic hydrogen evolution material and a preparation method thereof, wherein the material has high electrocatalytic hydrogen evolution performance.
In order to achieve the purpose of the invention, the technical scheme adopted by the invention is as follows:
a two-dimensional metal organic framework/molybdenum disulfide nano composite electro-catalysis hydrogen evolution material comprises two-dimensional metal organic framework nanosheets M-TCPP and molybdenum disulfide nanosheets MoS which are mutually dispersed2Wherein M is selected from Co2+、Ni2+Is 5,10,15, 20-tetrakis (4-carboxy-phenyl) -porphyrin, the molar ratio of M to Mo ions being 1: 0.4 to 8.
A preparation method of the two-dimensional metal organic framework/molybdenum disulfide nano composite electrocatalytic hydrogen evolution material comprises the following steps:
(1) synthesizing a two-dimensional metal organic framework nanosheet M-TCPP, wherein M is selected from Co2+、Ni2+TCPP is 5,10,15, 20-tetrakis (4-carboxy-phenyl) -porphyrin; dispersing the two-dimensional metal organic framework nanosheet in a dispersing agent to prepare a dispersion liquid A;
(2) synthesis of molybdenum disulfide nanosheet MoS2Dispersing the molybdenum disulfide nanosheets in a dispersing agent to prepare a dispersion liquid B;
(3) and dropwise adding the dispersion liquid A into the dispersion liquid B, carrying out ultrasonic treatment, stirring, separating and drying to obtain the two-dimensional metal organic framework/molybdenum disulfide nano composite electro-catalytic hydrogen evolution material.
Preferably, the two-dimensional metal organic framework nanosheet is synthesized by a solvothermal method; the molybdenum disulfide nanosheet is synthesized by a hydrothermal method.
Preferably, the solvothermal method is to drop an organic ligand solution into a metal ion solution, perform solvothermal reaction at 80 ℃, and obtain the two-dimensional metal organic framework nanosheet through separation and purification.
Preferably, the hydrothermal method is to perform hydrothermal reaction at 180 ℃ by taking soluble molybdate as a molybdenum source and L-cysteine as a sulfur source, and obtain the molybdenum disulfide nanosheet through separation and purification.
Preferably, the dispersant is ethanol.
Preferably, the ultrasonic treatment time in the step (3) is 25 minutes, and the stirring time is 12 hours.
The invention has the beneficial effects that: the preparation method provided by the invention is to introduce two-dimensional Metal Organic Framework (MOF) nanosheets into MoS2Preparing a two-dimensional metal organic framework/molybdenum disulfide nano composite electro-catalytic hydrogen evolution material two-dimensional MOF/MoS from nano sheets2The ultra-thin thickness, large specific surface area and fast electron transmission performance of the two-dimensional MOF are utilized to increase hydrogen evolution reaction active sites and specific surface area on the surface of the material, so that the electrocatalytic hydrogen evolution performance of the material is improved, and meanwhile, transition metal ions Co2+Or Ni2+Can enhance MoS2Conductivity of (2), regulation of MoS2The electro-catalysis hydrogen evolution performance of the structure is improved, and the two-dimensional MOF nano-sheet and the MoS are used2The electrocatalytic hydrogen evolution performance of the two-dimensional metal organic framework/molybdenum disulfide nano composite electrocatalytic hydrogen evolution material can be obviously improved due to the synergistic interaction of the nano sheets, and a new method is provided for developing an electrocatalytic hydrogen evolution catalyst with low price and high efficiency.
Drawings
FIG. 1. the two-dimensional Co-MOF/MoS2-3 and two-dimensional Co-MOF nanosheet and MoS2Comparison graph of electrocatalytic hydrogen evolution performance of the nanosheets.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the technical solutions of the present invention are described below clearly and completely, and it is obvious that the described embodiments are some, not all embodiments of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
In the following examples, BPY is 4,4 '-bipyridine, PVP is polyvinylpyrrolidone, DMF is N, N' -dimethylformamide and TCPP is 5,10,15, 20-tetrakis (4-carboxy-phenyl) -porphyrin.
Example 1
The preparation method of the two-dimensional metal organic framework/molybdenum disulfide nano composite electrocatalytic hydrogen evolution material comprises the following steps:
(1) 4.4mg of Co (NO)3)2·6H2O, 1.6mg BPY, 10mg PVP are added to a mixture of 4.5ml DMF and 1.5ml absolute ethanol, magnetic stirring is carried out until the solution is completely dissolved to obtain a solution (1), 4mg TCPP is weighed and added to a mixture of 1.5ml DMF and 0.5ml absolute ethanol, ultrasonic treatment is carried out for 15 minutes until the solution is completely dissolved to obtain a solution (2), then the solution (2) is dropwise added to the solution (1), after ultrasonic treatment for 25 minutes, the solution is transferred to a 18ml Teflon-lined reactor, the temperature of an oven is adjusted to 80 ℃, and the oven is placed in the oven to react for 24 hours. Naturally cooling to room temperature, performing centrifugal separation to obtain red precipitate, washing with ethanol twice to obtain two-dimensional Co-MOF nanosheets, and dispersing the two-dimensional Co-MOF nanosheets into 0.5ml of ethanol to form a dispersion liquid A;
(2) 0.4g of Na2MoO40.65g L cysteine and 60mL deionized water, then sealed in a 100mL Teflon-lined reactor and heated at 180 ℃ for 18 hours, after the reaction cooled naturally to room temperature, the black precipitate was collected by centrifugation, washed 2 times with deionized water and ethanol, and dried under vacuum at 80 ℃ for 12 hours to obtain MoS2Nanosheets prepared by mixing 10mg of the MoS2Nano meterDispersing the tablets into 20ml of ethanol to obtain a dispersion liquid B;
(3) dropwise adding the dispersion liquid A into the dispersion liquid B, carrying out ultrasonic treatment for 20 minutes, finally stirring at room temperature for 12 hours, carrying out centrifugal separation to collect the obtained precipitate, washing with ethanol for a plurality of times, and then carrying out vacuum drying at 80 ℃ for 10 hours to obtain the nano composite Co-MOF/MoS2-3。
Example 2
The same procedure as in example 1 was used to prepare a nanocomposite Co-MOF/MoS2-1, except that in step (2) 1mg of said MoS is added2The nanosheets were dispersed in 20ml of ethanol to give a dispersion B.
Example 3
The same procedure as in example 1 was used to prepare a nanocomposite Co-MOF/MoS2-2, except that in step (2) 5mg of said MoS is added2The nanosheets were dispersed in 20ml of ethanol to give a dispersion B.
Example 4
The same procedure as in example 1 was used to prepare a nanocomposite Co-MOF/MoS2-4, except that in step (2) 20mg of said MoS is added2The nanosheets were dispersed in 20ml of ethanol to give a dispersion B.
Example 5
The same procedure as in example 1 was used to prepare a nanocomposite Ni-MOF/MoS2-1 except that in step (1) 4.4mg of Ni (NO)3)2·6H2O, 1.6mg BPY, 10mg PVP were added to a mixture of 4.5ml DMF and 1.5ml absolute ethanol, and in step (2) 1mg of the MoS was added2The nanosheets were dispersed in 20ml of ethanol to give a dispersion B.
Example 6
The same procedure as in example 1 was used to prepare a nanocomposite Ni-MOF/MoS2-2 except that in step (1) 4.4mg of Ni (NO)3)2·6H2O, 1.6mg BPY, 10mg PVP were added to a mixture of 4.5ml DMF and 1.5ml absolute ethanol, 5mg of the MoS in step (2)2The nanosheets were dispersed in 20ml of ethanol to give a dispersion B.
Example 7
The same procedure as in example 1 was used to prepare a nanocomposite Ni-MOF/MoS2-3, except that in step (1) 4.4mg of Ni (NO)3)2·6H2O, 1.6mg BPY, 10mg PVP were added to a mixture of 4.5ml DMF and 1.5ml absolute ethanol.
Example 8
The same procedure as in example 1 was used to prepare a nanocomposite Ni-MOF/MoS24, except that in step (1) 4.4mg of Ni (NO)3)2·6H2O, 1.6mg BPY, 10mg PVP were added to a mixture of 4.5ml DMF and 1.5ml absolute ethanol, 20mg of the MoS in step (2)2The nanosheets were dispersed in 20ml of ethanol to give a dispersion B.
Example 9
Nanocomposite Co was prepared using the same procedure as in example 10.25Ni0.75-MOF/MoS2-1 except that in step (1) 1.1mg of Co (NO)3)2·6H2O、3.3mg Ni(NO3)2·6H2O, 1.6mg BPY, 10mg PVP were added to a mixture of 4.5ml DMF and 1.5ml absolute ethanol, and in step (2) 1mg of the MoS was added2The nanosheets were dispersed in 20ml of ethanol to give a dispersion B.
Example 10
Nanocomposite Co was prepared using the same procedure as in example 10.25Ni0.75-MOF/MoS2-2 except that in step (1) 1.1mg Co (NO)3)2·6H2O、3.3mg Ni(NO3)2·6H2O, 1.6mg BPY, 10mg PVP were added to a mixture of 4.5ml DMF and 1.5ml absolute ethanol, 5mg of the MoS in step (2)2The nanosheets were dispersed in 20ml of ethanol to give a dispersion B.
Example 11
Nanocomposite Co was prepared using the same procedure as in example 10.25Ni0.75-MOF/MoS2-3, except that in step (1) 1.1mg of Co (NO)3)2·6H2O、3.3mg Ni(NO3)2·6H2O, 1.6mg BPY, 10mg PVP 4.5ml DMF and 15ml of absolute ethyl alcohol mixture.
Example 12
Nanocomposite Co was prepared using the same procedure as in example 10.25Ni0.75-MOF/MoS2-4, except that in step (1) 1.1mg Co (NO)3)2·6H2O、3.3mg Ni(NO3)2·6H2O, 1.6mg BPY, 10mg PVP were added to a mixture of 4.5ml DMF and 1.5ml absolute ethanol, 20mg of the MoS in step (2)2The nanosheets were dispersed in 20ml of ethanol to give a dispersion B.
Example 13
Nanocomposite Co was prepared using the same procedure as in example 10.5Ni0.5-MOF/MoS2-1 except that in step (1) 2.2mg of Co (NO)3)2·6H2O、2.2mg Ni(NO3)2·6H2O, 1.6mg BPY, 10mg PVP were added to a mixture of 4.5ml DMF and 1.5ml absolute ethanol, and in step (2) 1mg of the MoS was added2The nanosheets were dispersed in 20ml of ethanol to give a dispersion B.
Example 14
Nanocomposite Co was prepared using the same procedure as in example 10.5Ni0.5-MOF/MoS2-2 except that in step (1) 2.2mg of Co (NO)3)2·6H2O、2.2mg Ni(NO3)2·6H2O, 1.6mg BPY, 10mg PVP were added to a mixture of 4.5ml DMF and 1.5ml absolute ethanol, 5mg of the MoS in step (2)2The nanosheets were dispersed in 20ml of ethanol to give a dispersion B.
Example 15
Nanocomposite Co was prepared using the same procedure as in example 10.5Ni0.5-MOF/MoS2-3 except that in step (1) 2.2mg of Co (NO)3)2·6H2O、2.2mg Ni(NO3)2·6H2O, 1.6mg BPY, 10mg PVP were added to a mixture of 4.5ml DMF and 1.5ml absolute ethanol.
Example 16
The same procedure as in example 1 was followedPreparation of nanocomposite Co0.5Ni0.5-MOF/MoS2-4, except that in step (1) 2.2mg of Co (NO)3)2·6H2O、2.2mg Ni(NO3)2·6H2O, 1.6mg BPY, 10mg PVP were added to a mixture of 4.5ml DMF and 1.5ml absolute ethanol, 20mg of the MoS in step (2)2The nanosheets were dispersed in 20ml of ethanol to give a dispersion B.
Example 17
Nanocomposite Co was prepared using the same procedure as in example 10.75Ni0.25-MOF/MoS2-1 except that in step (1) 3.3mg Co (NO)3)2·6H2O、1.1mg Ni(NO3)2·6H2O, 1.6mg BPY, 10mg PVP were added to a mixture of 4.5ml DMF and 1.5ml absolute ethanol, and in step (2) 1mg of the MoS was added2The nanosheets were dispersed in 20ml of ethanol to give a dispersion B.
Example 18
Nanocomposite Co was prepared using the same procedure as in example 10.75Ni0.25-MOF/MoS2-2 except that in step (1) 3.3mg Co (NO)3)2·6H2O、1.1mg Ni(NO3)2·6H2O, 1.6mg BPY, 10mg PVP were added to a mixture of 4.5ml DMF and 1.5ml absolute ethanol, 5mg of the MoS in step (2)2The nanosheets were dispersed in 20ml of ethanol to give a dispersion B.
Example 19
Nanocomposite Co was prepared using the same procedure as in example 10.75Ni0.25-MOF/MoS2-3, except that in step (1) 3.3mg Co (NO)3)2·6H2O、1.1mg Ni(NO3)2·6H2O, 1.6mg BPY, 10mg PVP were added to a mixture of 4.5ml DMF and 1.5ml absolute ethanol.
Example 20
Nanocomposite Co was prepared using the same procedure as in example 10.75Ni0.25-MOF/MoS2-4, except that in step (1) 3.3mg Co (NO)3)2·6H2O、1.1mg Ni(NO3)2·6H2O, 1.6mg BPY, 10mg PVP were added to a mixture of 4.5ml DMF and 1.5ml absolute ethanol, 20mg of the MoS in step (2)2The nanosheets were dispersed in 20ml of ethanol to give a dispersion B.
Test example
The electrocatalytic hydrogen evolution performance of the material prepared in example 1 was tested using the Shanghai Chenghua CHI660E electrochemical workstation, and all potential values were converted to relatively Reversible Hydrogen Electrode (RHE) voltages by adding (0.2415+0.059pH) V. The test was carried out using a three-electrode system, a glassy carbon electrode (diameter 3mm, area 0.070785 cm)2) The working electrode, the counter electrode and the reference electrode are respectively a platinum wire and silver-silver chloride (3M KCl), and the electrolyte is 0.5mol/L sulfuric acid solution. The relevant settings of the linear scan test parameters are as follows: the scanning range is from 0.1 to 0.6V (vs. RHE), the linear scanning speed is 5mV/s, and the sampling interval is 1 mV.
The working electrode was prepared as follows: first, 0.05 μm Al was used for a glassy carbon electrode on a chamois2O3Polishing the polishing powder for 15min, cleaning with absolute ethyl alcohol in an ultrasonic machine for 2min, then ultrasonically cleaning in distilled water for two times, each for 2min, obtaining a bright mirror surface, and then drying for later use. Weighing 4mg of dried Co-MOF/MoS2-3 samples 16 μ L of 5 wt% Nafion and 1mL of dispersion were added, and 5 μ L of the catalyst dispersion drop was pipetted onto the surface of the polished glassy carbon electrode and allowed to air dry at room temperature for future use.
FIG. 1 shows Co-MOF/MoS under the same conditions2-3、MoS2The electrocatalytic hydrogen evolution performance of the nano-sheet and the two-dimensional Co-MOF nano-sheet shows that Co-MOF/MoS2-3 nanocomposite material exhibiting a MoS ratio2The nano-sheet and the two-dimensional Co-MOF nano-sheet have better electro-catalytic hydrogen evolution activity. Mixing MoS2After being combined with a two-dimensional Co-MOF nano sheet, the composite nano material has high activity on HER. The lowest initial potential for starting hydrogen evolution is about 170mV, above which the cathodic current rises rapidly to 10mA + cm at 262mV-2。
Finally, it should be noted that: the above examples are only intended to illustrate the technical solution of the present invention, but not to limit it; although the present invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some technical features may be equivalently replaced; and such modifications or substitutions do not depart from the spirit and scope of the corresponding technical solutions of the embodiments of the present invention.

Claims (7)

1. The two-dimensional metal organic framework/molybdenum disulfide nano composite electro-catalytic hydrogen evolution material is characterized by comprising two-dimensional metal organic framework nanosheets M-TCPP and molybdenum disulfide nanosheets MoS which are mutually dispersed2Wherein M is selected from Co2+、Ni2+Is 5,10,15, 20-tetrakis (4-carboxy-phenyl) -porphyrin, the molar ratio of M to Mo ions being 1: 0.4 to 8.
2. A method for preparing the two-dimensional metal organic framework/molybdenum disulfide nano composite electrocatalytic hydrogen evolution material as set forth in claim 1, which comprises the following steps:
(1) synthesizing a two-dimensional metal organic framework nanosheet M-TCPP, wherein M is selected from Co2+、Ni2+TCPP is 5,10,15, 20-tetrakis (4-carboxy-phenyl) -porphyrin; dispersing the two-dimensional metal organic framework nanosheet in a dispersing agent to prepare a dispersion liquid A;
(2) synthesis of molybdenum disulfide nanosheet MoS2Dispersing the molybdenum disulfide nanosheets in a dispersing agent to prepare a dispersion liquid B;
(3) and dropwise adding the dispersion liquid A into the dispersion liquid B, carrying out ultrasonic treatment, stirring, separating and drying to obtain the two-dimensional metal organic framework/molybdenum disulfide nano composite electro-catalytic hydrogen evolution material.
3. The preparation method of the two-dimensional metal organic framework/molybdenum disulfide nanocomposite electrocatalytic hydrogen evolution material as claimed in claim 2, wherein the two-dimensional metal organic framework nanosheet is synthesized by a solvothermal method; the molybdenum disulfide nanosheet is synthesized by a hydrothermal method.
4. The preparation method of the two-dimensional metal organic framework/molybdenum disulfide nanocomposite hydrogen evolution material according to claim 3, wherein the solvothermal method comprises the steps of dropwise adding an organic ligand solution into a metal ion solution, carrying out solvothermal reaction at 80 ℃, and separating and purifying to obtain the two-dimensional metal organic framework nanosheet.
5. The preparation method of the two-dimensional metal organic framework/molybdenum disulfide nano composite electrocatalytic hydrogen evolution material as claimed in claim 3, wherein the hydrothermal method is to perform hydrothermal reaction at 180 ℃ by taking soluble molybdate as a molybdenum source and L-cysteine as a sulfur source, and obtain a molybdenum disulfide nanosheet through separation and purification.
6. The preparation method of the two-dimensional metal organic framework/molybdenum disulfide nanocomposite electrocatalytic hydrogen evolution material as claimed in claim 2, wherein in the step (1) and the step (2), the dispersant is ethanol.
7. The preparation method of the two-dimensional metal organic framework/molybdenum disulfide nano composite electro-catalytic hydrogen evolution material as claimed in claim 2, wherein the ultrasonic treatment time in step (3) is 25 minutes, and the stirring time is 12 hours.
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