CN108546924B - Molybdenum diselenide/graphite composite material and preparation method and application thereof - Google Patents

Molybdenum diselenide/graphite composite material and preparation method and application thereof Download PDF

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CN108546924B
CN108546924B CN201810457292.XA CN201810457292A CN108546924B CN 108546924 B CN108546924 B CN 108546924B CN 201810457292 A CN201810457292 A CN 201810457292A CN 108546924 B CN108546924 B CN 108546924B
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graphite
molybdenum
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molybdenum diselenide
graphite composite
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CN108546924A (en
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邹俭鹏
冒旭
李丹妮
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Central South University
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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
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    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
    • C23C14/34—Sputtering
    • C23C14/35—Sputtering by application of a magnetic field, e.g. magnetron sputtering
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • C23C14/14—Metallic material, boron or silicon
    • C23C14/16—Metallic material, boron or silicon on metallic substrates or on substrates of boron or silicon
    • C23C14/165—Metallic material, boron or silicon on metallic substrates or on substrates of boron or silicon by cathodic sputtering
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/58—After-treatment
    • C23C14/5846—Reactive treatment
    • C23C14/5866—Treatment with sulfur, selenium or tellurium
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B1/00—Electrolytic production of inorganic compounds or non-metals
    • C25B1/01—Products
    • C25B1/02—Hydrogen or oxygen
    • C25B1/04—Hydrogen or oxygen by electrolysis of water
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
    • C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • 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 discloses a molybdenum diselenide/graphite composite material which is composed of molybdenum diselenide nanosheets and graphite, wherein the molybdenum diselenide nanosheets vertically grow on the surface of the graphite, the content of molybdenum diselenide is 0.04-10 vol%, and the content of graphite is 90-99.96 vol%. The molybdenum diselenide/graphite composite material provided by the invention vertically grows on the surface of a molybdenum diselenide nanosheet on the graphite surface and consists of a plurality of suspension bonds, in the application of electrolytic hydrogen production and electrocatalysis, the surfaces of the suspension bonds are active sites, the adopted graphite matrix has a porous layered structure, so that a larger specific surface area is provided, the number of the active sites of the catalyst is increased, and the activity of hydrogen evolution reaction can be improved; the preparation method has simple flow, short preparation time and low cost, and can be used for large-scale industrial production; the molybdenum diselenide/graphite composite material has good and stable catalytic performance, small Tafel coefficient, low hydrogen evolution overpotential and wide application prospect in the field of electrolysis of water and hydrogen evolution.

Description

Molybdenum diselenide/graphite composite material and preparation method and application thereof
Technical Field
The invention belongs to the technical field of preparation of electrocatalytic materials, and particularly relates to a molybdenum diselenide/graphite composite material as well as a preparation method and application thereof.
Background
Molybdenum diselenide (MoSe)2) The transition metal two-dimensional layered material has excellent catalytic performance, magnetism, semiconductor properties and the like, and has good application prospects in the fields of photoelectricity, catalysis, superconduction and the like. Molybdenum diselenide has a sheet structure similar to graphene, Mo atoms and Se atoms in layers are combined through covalent bonds, the layers are connected through Van der Waals force, and the layers are easily stripped, so that the conductivity of the molybdenum diselenide is poor, and further application of the molybdenum diselenide is directly limited.
In order to improve the electrochemical performance of molybdenum diselenide, graphene and carbon nanotubes with high specific surface area, high conductivity and excellent mechanical properties are utilized to prepare the composite material, and the composite material can be widely applied to electronic devices, new energy electrode materials and catalytic materials. Hui Yang (chem. Lett,2016,45:69-71) discloses electrospinningPreparing PAN nano fiber film, carbonizing to obtain CNFs, and performing Chemical Vapor Deposition (CVD) to MoSe2MoSe is prepared by loading on CNFs substrate2the/CNFs composite material is used as a cathode of the electrocatalytic hydrogen evolution reaction. Shun Mao discloses a particular MoSe in (Small,2015,11(4):414)2The graphene composite material is prepared by firstly preparing graphene by Plasma Enhanced Chemical Vapor Deposition (PECVD) in-situ growth and then preparing MoSe by using a Chemical Vapor Deposition (CVD) method2Grown onto a graphene substrate.
However, the above-mentioned techniques have drawbacks and disadvantages: (1) the graphene and the carbon nano tube are expensive, the preparation process is easy to agglomerate, and the dispersion effect is poor; (2) the process is complex, the operation steps are more, the time consumption is longer, the preparation efficiency is lower, and the large-scale popularization and application are difficult.
Disclosure of Invention
The invention aims to provide a molybdenum diselenide/graphite composite material and a preparation method and application thereof, so as to reduce the production cost and shorten the preparation period.
The molybdenum diselenide/graphite composite material provided by the invention comprises molybdenum diselenide nanosheets and graphite, wherein the molybdenum diselenide nanosheets vertically grow on the surface of the graphite to form a molybdenum diselenide layer, the content of molybdenum diselenide is 0.04-10 vol%, and the content of the graphite is 90-99.96 vol%.
Preferably, the thickness of the molybdenum diselenide layer is 200 nm-10 um, and the thickness of the graphite is 500-1000 um.
The invention also provides a preparation method of the molybdenum diselenide/graphite composite material, which comprises the following steps: generating a molybdenum film on the surface of graphite by using direct-current magnetron sputtering to obtain a molybdenum/graphite composite material; and carrying out rapid selenization treatment on the molybdenum/graphite composite material to obtain the molybdenum diselenide/graphite composite material.
Preferably, the preparation method of the molybdenum diselenide/graphite composite material comprises the following steps:
(1) pretreatment of graphite: sequentially putting graphite into acetone and absolute ethyl alcohol, carrying out ultrasonic treatment for 5-60 min, and drying to obtain pretreated graphite;
(2) d, direct-current magnetron sputtering molybdenum film: placing the pretreated graphite obtained in the step (1) in a magnetron sputtering chamber, and vacuumizing the magnetron sputtering chamber to 8.0 x 10-4Under Pa, taking argon as working gas, taking a molybdenum target as a sputtering source, controlling the pressure of the argon to be 0.2 Pa-5.0 Pa, and performing direct-current magnetron sputtering to generate a molybdenum film on the surface of graphite to obtain a molybdenum/graphite composite material;
(3) and (3) rapid selenization: placing selenium powder in a corundum crucible, placing the molybdenum/graphite composite material obtained in the step (2) in a container formed by reversely buckling two corundum boats together, enabling one surface of a molybdenum film of graphite to face upwards, then placing the container in which the selenium powder and the molybdenum/graphite composite material are placed under the conditions that the vacuum degree is below 0.8Pa and the temperature is 400-800 ℃, and carrying out heat treatment for 5-40 min to enable molybdenum diselenide nanosheets to vertically grow on the surface of graphite, so as to obtain the molybdenum diselenide/graphite composite material.
Preferably, in the step (1), the graphite after ultrasonic treatment is placed in a vacuum drying oven at 50-80 ℃ for 0.5-2 h.
Preferably, in the step (2), the distance between the molybdenum target material and the graphite is 5-15 cm.
Preferably, in the step (2), the power of the direct current magnetron sputtering is 30-150W, the bias voltage is-200-0V, and the time of the direct current magnetron sputtering is 1-30 min.
Preferably, in the step (2), the temperature of the graphite is 25-450 ℃ in the direct current magnetron sputtering process.
Preferably, in the step (3), the heat treatment is performed by a tube furnace, and the tube furnace comprises a quartz tube which can be vacuumized.
Preferably, the purity of the argon is not lower than 99.99%, and the purity of the molybdenum target is not lower than 99.99%.
The invention provides application of the molybdenum diselenide/graphite composite material, and the molybdenum diselenide/graphite composite material is applied to an electrolytic water hydrogen evolution electrode material.
Compared with the prior art, the invention has the beneficial technical effects that:
(1) the molybdenum diselenide/graphite composite material provided by the invention vertically grows on the surface of a molybdenum diselenide nanosheet on the graphite surface and consists of a plurality of dangling bonds, and in the application of electrolytic hydrogen production and electrocatalysis, the surface of the dangling bond is an active site, so that the number of the active sites of a catalyst is increased, and the activity of hydrogen evolution reaction can be improved.
(2) The preparation method disclosed by the invention has the advantages that the molybdenum film is generated on the surface of the graphite substrate through direct-current magnetron sputtering, and then the molybdenum diselenide/graphite composite material is obtained through rapid selenization.
(3) The graphite matrix adopted by the invention has a porous layered structure, so that a larger specific surface area is provided, the number of active sites is increased, the electrocatalytic efficiency is improved, the prepared molybdenum diselenide/graphite composite material has better and more stable catalytic performance, a smaller Tafel coefficient and a lower hydrogen evolution overpotential, and has a wide application prospect in the field of hydrogen evolution by electrolyzing water.
Drawings
Fig. 1 is an SEM image of a molybdenum diselenide/graphite composite material obtained in example 1 of the present invention.
Fig. 2 is an SEM image of the molybdenum diselenide/graphite composite material obtained in example 2 of the present invention.
Fig. 3 is an SEM image of the molybdenum diselenide/graphite composite material obtained in example 3 of the present invention.
Fig. 4 is a hydrogen evolution polarization curve diagram of molybdenum diselenide/graphite electrode electrolysis water obtained in embodiments 1 to 3 of the present invention.
FIG. 5 shows the Tafel slope of water electrolysis hydrogen evolution of molybdenum diselenide/graphite electrode obtained in examples 1 to 3 of the present invention.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, rather than all embodiments, and all other embodiments obtained by those skilled in the art without any creative work based on the embodiments of the present invention belong to the protection scope of the present invention.
The invention is further described with reference to the following figures and specific examples.
Example 1
The invention provides a preparation method of a molybdenum diselenide/graphite composite material, which comprises the following steps:
(1) pretreatment of graphite: sequentially putting a graphite substrate with the thickness of 20mm multiplied by 10mm multiplied by 1mm (length multiplied by width multiplied by thickness) into acetone and absolute ethyl alcohol, carrying out ultrasonic treatment for 15min, and drying in a vacuum drying oven at the temperature of 60 ℃ for 1h to obtain pretreated graphite;
(2) d, direct-current magnetron sputtering molybdenum film: after the pretreated graphite is placed in a magnetron sputtering chamber, a high-purity molybdenum target material (99.99%) with the diameter of 60mm is adopted, and the magnetron sputtering chamber is vacuumized to 8.0 multiplied by 10-4The distance between the molybdenum target and the graphite substrate is 12cm under Pa, no sputtering bias is generated, the substrate temperature is 25 ℃, high-purity argon (99.999%) is used as working gas, the sputtering power is 60W, the working pressure is adjusted to 2.0Pa, the molybdenum film is sputtered for 5min, and the molybdenum/graphite composite material is obtained;
(3) and (3) rapid selenization: weighing 1.4g of selenium powder, placing the selenium powder in a corundum crucible of 3ml, placing a molybdenum/graphite composite material in a container formed by reversely buckling two corundum boats together, enabling one surface of a molybdenum film of a graphite substrate to face upwards, then placing the container formed by the corundum crucible and the two corundum boats in a tube furnace, vacuumizing a quartz tube of the tube furnace to be below 0.8Pa by using a mechanical vacuum pump, firstly heating a sample area to 500 ℃, then pushing the sample to the sample area for rapid heating, preserving heat for 15min, pushing the sample away from the sample area after heating, turning off a power supply, and naturally cooling the sample to room temperature to obtain the molybdenum diselenide/graphite composite material.
Example 2
The invention provides a preparation method of a molybdenum diselenide/graphite composite material, which comprises the following steps:
(1) pretreatment of graphite: sequentially putting a graphite substrate with the thickness of 20mm multiplied by 10mm multiplied by 1mm (length multiplied by width multiplied by thickness) into acetone and absolute ethyl alcohol, carrying out ultrasonic treatment for 30min, and drying in a vacuum drying oven at the temperature of 80 ℃ for 0.5h to obtain pretreated graphite;
(2) d, direct-current magnetron sputtering molybdenum film: after the pretreated graphite is placed in a magnetron sputtering chamber, a high-purity molybdenum target material (99.99%) with the diameter of 60mm is adopted, and the magnetron sputtering chamber is vacuumized to 8.0 multiplied by 10-4The distance between the molybdenum target and the graphite substrate is 12cm under Pa, no sputtering bias is generated, the substrate temperature is 25 ℃, high-purity argon (99.999%) is used as working gas, the sputtering power is 60W, the working pressure is adjusted to 2.0Pa, the molybdenum film is sputtered for 5min, and the molybdenum/graphite composite material is obtained;
(3) and (3) rapid selenization: weighing 1.4g of selenium powder, placing the selenium powder in a corundum crucible of 3ml, placing a molybdenum/graphite composite material in a container formed by reversely buckling two corundum boats together, enabling one surface of a molybdenum film of a graphite substrate to face upwards, then placing the container formed by the corundum crucible and the two corundum boats in a tube furnace, vacuumizing a quartz tube of the tube furnace to be below 0.8Pa by using a mechanical vacuum pump, firstly heating a sample area to 500 ℃, then pushing the sample to the sample area for rapid heating, preserving heat for 5min, pushing the sample away from the sample area after heating, turning off a power supply, and naturally cooling the sample to room temperature to obtain the molybdenum diselenide/graphite composite material.
Example 3
The invention provides a preparation method of a molybdenum diselenide/graphite composite material, which comprises the following steps:
(1) pretreatment of graphite: sequentially putting a graphite substrate with the thickness of 20mm multiplied by 10mm multiplied by 1mm (length multiplied by width multiplied by thickness) into acetone and absolute ethyl alcohol, carrying out ultrasonic treatment for 60min, and drying in a vacuum drying oven at the temperature of 50 ℃ for 1h to obtain pretreated graphite;
(2) d, direct-current magnetron sputtering molybdenum film: after the pretreated graphite is placed in a magnetron sputtering chamber, a high-purity molybdenum target material (99.99%) with the diameter of 60mm is adopted, and the magnetron sputtering chamber is vacuumized to 8.0 multiplied by 10-4The distance between the molybdenum target and the graphite substrate is 12cm under Pa, no sputtering bias is generated, the substrate temperature is 25 ℃, high-purity argon (99.999%) is used as working gas, the sputtering power is 60W, the working pressure is adjusted to 2.0Pa, the molybdenum film is sputtered for 5min, and the molybdenum/graphite composite material is obtained;
(3) and (3) rapid selenization: weighing 1.4g of selenium powder, placing the selenium powder in a corundum crucible of 3ml, placing a molybdenum/graphite composite material in a container formed by reversely buckling two corundum boats together, enabling one surface of a molybdenum film of a graphite substrate to face upwards, then placing the container formed by the corundum crucible and the two corundum boats in a tube furnace, vacuumizing a quartz tube of the tube furnace to be below 0.8Pa by using a mechanical vacuum pump, firstly heating a sample area to 500 ℃, then pushing the sample to the sample area for rapid heating, preserving heat for 25min, pushing the sample away from the sample area after heating, turning off a power supply, and naturally cooling the sample to room temperature to obtain the molybdenum diselenide/graphite composite material.
Example 4
The invention provides a preparation method of a molybdenum diselenide/graphite composite material, which comprises the following steps:
(1) pretreatment of graphite: sequentially putting a graphite substrate with the thickness of 20mm multiplied by 10mm multiplied by 1mm (length multiplied by width multiplied by thickness) into acetone and absolute ethyl alcohol, carrying out ultrasonic treatment for 60min, and drying in a vacuum drying oven at the temperature of 80 ℃ for 0.5h to obtain pretreated graphite;
(2) d, direct-current magnetron sputtering molybdenum film: after the pretreated graphite is placed in a magnetron sputtering chamber, a high-purity molybdenum target material (99.99%) with the diameter of 60mm is adopted, and the magnetron sputtering chamber is vacuumized to 8.0 multiplied by 10-4The distance between the molybdenum target and the graphite substrate is 8cm under Pa, no sputtering bias voltage exists, the substrate temperature is 200 ℃, high-purity argon (99.999%) is used as working gas, the sputtering power is 40W, the working pressure is adjusted to 4.0Pa for sputtering for 10min, and a molybdenum film is generated on the surface of the graphite substrate to obtain a molybdenum/graphite composite material;
(3) and (3) rapid selenization: weighing 1.4g of selenium powder, placing the selenium powder in a corundum crucible of 3ml, placing a molybdenum/graphite composite material in a container formed by reversely buckling two corundum boats together, enabling one surface of a molybdenum film of a graphite substrate to face upwards, then placing the container formed by the corundum crucible and the two corundum boats in a tube furnace, vacuumizing a quartz tube of the tube furnace to be below 0.8Pa by using a mechanical vacuum pump, firstly heating a sample area to 800 ℃, then pushing the sample to the sample area for rapid heating, preserving heat for 10min, pushing the sample away from the sample area after heating, turning off a power supply, and naturally cooling the sample to room temperature to obtain the molybdenum diselenide/graphite composite material.
Example 5
The invention provides a preparation method of a molybdenum diselenide/graphite composite material, which comprises the following steps:
(1) pretreatment of graphite: sequentially putting a graphite substrate with the thickness of 20mm multiplied by 10mm multiplied by 1mm (length multiplied by width multiplied by thickness) into acetone and absolute ethyl alcohol, carrying out ultrasonic treatment for 5min, and drying in a vacuum drying oven at the temperature of 60 ℃ for 2h to obtain pretreated graphite;
(2) d, direct-current magnetron sputtering molybdenum film: after the pretreated graphite is placed in a magnetron sputtering chamber, a high-purity molybdenum target material (99.99%) with the diameter of 60mm is adopted, and the magnetron sputtering chamber is vacuumized to 8.0 multiplied by 10-4The distance between the molybdenum target and the graphite substrate is 15cm under Pa, no sputtering bias voltage exists, the substrate temperature is 400 ℃, high-purity argon (99.999%) is used as working gas, the sputtering power is 150W, the working pressure is adjusted to 0.5Pa, the molybdenum film is sputtered for 3min, and the molybdenum/graphite composite material is obtained;
(3) and (3) rapid selenization: weighing 1.4g of selenium powder, placing the selenium powder in a corundum crucible of 3ml, placing a molybdenum/graphite composite material in a container formed by reversely buckling two corundum boats together, enabling one surface of a molybdenum film of a graphite substrate to face upwards, then placing the container formed by the corundum crucible and the two corundum boats in a tube furnace, vacuumizing a quartz tube of the tube furnace to be below 0.8Pa by using a mechanical vacuum pump, firstly heating a sample area to 700 ℃, then pushing the sample to the sample area for rapid heating, preserving heat for 10min, pushing the sample away from the sample area after heating, turning off a power supply, and naturally cooling the sample to room temperature to obtain the molybdenum diselenide/graphite composite material.
Application example 1
The invention provides an application of a molybdenum diselenide/graphite composite material, which is applied to an electrolytic water hydrogen evolution electrode material in the molybdenum diselenide/graphite composite material prepared in the embodiment 1-3.
The preparation process of the electrode material comprises the following steps: using an insulating tape to mix 20 × 10 × 1mm of MoSe2Encapsulating the/graphite composite material to enable MoSe2The exposed geometric area of the film was 1cm2(ii) a Simultaneously adding part of MoSe2Scraping the film with a blade to expose graphite material, and assembling into a Pt electrode clampOhmic contact is used as a working electrode to prepare the MoSe2A graphite working electrode.
The test method comprises the following steps: adopts the traditional three-electrode system at 0.5mol/L H2SO4And (4) carrying out hydrogen evolution reaction performance test in the electrolyte. All electrochemical tests were carried out at ambient temperature and pressure, MoSe2The graphite composite material is used as a working electrode, and the geometric working area of the working electrode is 1cm2The Saturated Calomel Electrode (SCE) is a reference electrode, the graphite rod is a counter electrode, and a Rujin capillary tube is added on the reference electrode for reducing the solution resistance.
In MoSe2Before the hydrogen evolution test of the graphite composite material, bubbles on the surface of an electrode are removed, and then the MoSe is tested by using a Cyclic Voltammetry (CV) test method2Pretreating the film, sweeping the electrode material for 10 CV cycles in a voltage range of 0-0.8V (vs RHE), and eliminating MoSe2Some contaminants adsorbed on the surface of the film make the electrode performance test more stable. The test range of linear sweep voltammetry is 0.1 to-0.7V (vs RHE), and the sweep rate is 5 mV/s. Evaluation of MoSe by Linear sweep voltammetry2The catalytic performance of the graphite electrode material can obtain hydrogen evolution potential, Tafel parameters and the like from a cathode polarization curve.
FIGS. 1, 2 and 3 are SEM images of the molybdenum diselenide/graphite composite material obtained in examples 1 to 3, and it can be seen from FIGS. 1 to 3 that a large amount of MoSe can be grown on the surface of graphite within 15min of selenization time2Vertical wafers (example 1), and shorter selenization time (5min) and longer selenization time (25min), the MoSe prepared2The number of vertical wafers is small, and as can be seen from fig. 1 to 3, the thickness of the molybdenum diselenide nanosheet is 10 to 25nm, the length is 100 to 200nm, and the height is 100 to 200 nm.
FIG. 4 is a graph showing the hydrogen evolution polarization curve of molybdenum diselenide/graphite electrode obtained in embodiments 1 to 3 of the present invention when the current density reaches 10mA cm-2When the overpotential is-125 mV (vs RHE) (example 1), 231mV (vs RHE) (example 2), and 207mV (vs RHE) (example 3), respectively, the catalytic hydrogen evolution activity of the molybdenum diselenide/graphite composite material obtained in example 1 is the highest.
FIG. 5 shows the Tafel slopes of water electrolysis hydrogen evolution from molybdenum diselenide/graphite electrodes obtained in examples 1 to 3 of the present invention, and the Tafel slopes are 52.1mV dec-1(example 1), 101.8mV dec-1(example 2), 99.2mV dec-1(example 3), it is demonstrated that the molybdenum diselenide/graphite electrode obtained in example 1 is most stable and has a good application prospect in the technical field of electrocatalytic materials.
The above description is only a preferred embodiment of the present invention, and the protection scope of the present invention is not limited to the above-described embodiments. Modifications and variations that may occur to those skilled in the art without departing from the spirit and scope of the invention are to be considered as within the scope of the invention.

Claims (8)

1. A preparation method of a molybdenum diselenide/graphite composite material is characterized by comprising the following steps:
(1) pretreatment of graphite: sequentially putting graphite into acetone and absolute ethyl alcohol, carrying out ultrasonic treatment for 5-60 min, and drying to obtain pretreated graphite;
(2) d, direct-current magnetron sputtering molybdenum film: placing the pretreated graphite obtained in the step (1) in a magnetron sputtering chamber, and vacuumizing the magnetron sputtering chamber to 8.0 x 10-4Under Pa, taking argon as working gas, taking a molybdenum target as a sputtering source, controlling the pressure of the argon to be 0.2-5.0 Pa, and performing direct-current magnetron sputtering to generate a molybdenum film on the surface of graphite to obtain a molybdenum/graphite composite material;
(3) and (3) rapid selenization: placing selenium powder in a corundum crucible, placing the molybdenum/graphite composite material obtained in the step (2) in a container formed by reversely buckling two corundum boats together, enabling one surface of a molybdenum film of graphite to face upwards, then placing the container in which the selenium powder and the molybdenum/graphite composite material are placed under the conditions that the vacuum degree is below 0.8Pa and the temperature is 400-800 ℃, and carrying out heat treatment for 15min to enable molybdenum diselenide nanosheets to vertically grow on the surface of the graphite, so as to obtain the molybdenum diselenide/graphite composite material;
the molybdenum diselenide/graphite composite material is composed of molybdenum diselenide nanosheets and graphite, the molybdenum diselenide nanosheets vertically grow on the surface of the graphite to form a molybdenum diselenide layer, the content of the molybdenum diselenide is 0.04-10 vol%, and the content of the graphite is 90-99.96 vol%.
2. The method for preparing a molybdenum diselenide/graphite composite material according to claim 1, wherein the thickness of the molybdenum diselenide layer is 200nm to 100 μm, and the thickness of the graphite is 500 to 1000 μm.
3. The preparation method of the molybdenum diselenide/graphite composite material according to claim 1, wherein in the step (1), the graphite subjected to ultrasonic treatment is placed in a vacuum drying oven at 50-80 ℃, and the drying time is 0.5-2 h.
4. The method for preparing a molybdenum diselenide/graphite composite material according to claim 1, wherein in the step (2), the distance between the molybdenum target material and the graphite is 5-15 cm.
5. The preparation method of the molybdenum diselenide/graphite composite material according to claim 1, wherein in the step (2), the power of the direct current magnetron sputtering is 30-150W, the bias voltage is-200-0V, and the time of the direct current magnetron sputtering is 1-30 min.
6. The method for preparing a molybdenum diselenide/graphite composite material according to claim 1, wherein in the step (2), the temperature of graphite is 25-450 ℃ in the direct current magnetron sputtering process.
7. The method for preparing a molybdenum diselenide/graphite composite material according to claim 1, wherein in the step (3), the heat treatment is performed by a tube furnace, and the tube furnace comprises a quartz tube which can be evacuated.
8. The use of the molybdenum diselenide/graphite composite material according to any one of claims 1 to 7, wherein the molybdenum diselenide/graphite composite material is used as an electrolytic water hydrogen evolution electrode material.
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