1. A transition metal compound hydrogen evolution thin film, characterized in that: the hydrogen evolution catalyst layer (2) is arranged on the surface of the substrate layer (1), and the hydrogen evolution catalyst layer (2) is a thin film formed by one of transition group metal sulfur compounds, transition group metal selenium compounds and transition group metal tellurium compounds.

2. The transition metal compound hydrogen evolution thin film according to claim 2, wherein the hydrogen evolution catalyst layer (2) is MoS₂、WS₂、MoSe₂、WSe₂、MoTe₂And WTE₂A film made of one of the above materials.

3. The transition group metal compound hydrogen evolution thin film according to claim 1, wherein the base layer (1) is made of metal or ceramic;

when the substrate layer (1) is metal, the metal is one of V, Nb, Ta, Mo, Ni, Ti, Pd, Pt, porous stainless steel, V/Ni alloy, V/Cr alloy, V/Cu alloy, V/Fe alloy, V/Al alloy, V/Co alloy, V/Mo alloy, V/W alloy, V/Ti/Ni alloy, V/Fe/Al alloy, V/Mo/W alloy, Nb/Ti/Ni alloy, Nb/Ti/Co alloy and Nb/Mo/W alloy;

when the substrate layer (1) is ceramic, the ceramic is one of porous alumina ceramic chip/tube, porous zirconia ceramic chip/tube and zeolite.

4. The method for preparing a hydrogen evolution thin film of a transition metal compound by radio frequency back-sputtering modification according to any one of claims 1 to 3, characterized by comprising the following steps:

the method comprises the following steps: pre-treating the substrate layer (1);

step two: cleaning the substrate layer (1) by using ion beams;

step three: forming a hydrogen evolution catalyst layer (2) on the surface of the substrate layer (1) by adopting one of chemical vapor deposition, hydrothermal synthesis, magnetron sputtering, ion beam sputtering, electron beam evaporation, pulse deposition, molecular beam epitaxy and atomic layer deposition;

step four: and irradiating and etching on the surface of the hydrogen evolution catalyst layer (2) by utilizing a radio frequency back sputtering mode.

5. The RF backsplash modification method for producing a hydrogen evolution thin film of a transition metal compound according to claim 4,

in the first step, the substrate layer is ultrasonically cleaned for 5-15min by sequentially adopting acetone and absolute ethyl alcohol, the ultrasonic cleaning is repeated for 2-3 times, then the substrate layer is washed for 1-2 min by using deionized water, and then the substrate layer is dried.

6. The RF back-sputtering modification preparation method of a hydrogen evolution thin film of a transition group metal compound as claimed in claim 4, wherein in step three, a hydrogen evolution catalyst layer is formed on the surface of the substrate layer by magnetron sputtering.

7. The RF backsplash modification method for producing a hydrogen evolution thin film of a transition metal compound according to claim 6,

the cleaning conditions in the second step include: the vacuum degree in the sputtering cavity is less than 10^-4Pa, substrate temperature of 25-600 deg.C, substrate negative bias of 0-300V, argon flow of 3-20sccm, working pressure of 0.2-1.0Pa, sputtering power of 0-300V, and irradiation time of 5-10 min.

The magnetron sputtering conditions of the step three comprise: the vacuum degree in the sputtering cavity is less than 10^-4Pa, the temperature of the basal layer is 25-600 ℃, the negative bias of the basal layer is 0-500V, the flow of introduced argon is 3-30sccm, the working pressure is 0.2-2.0Pa, the sputtering power is 0-300V, and the irradiation time is 5-100 min;

the conditions of the radio frequency back splash in the fourth step comprise: the vacuum degree in the sputtering cavity is less than 10^-4Pa, introducing argon gas flow of 3-70sccm, working pressure of 1.0-50Pa, sputtering power of 0-300V, and irradiation time of 0-5 min.

8. Use of a transition metal compound hydrogen evolution film according to any one of claims 1 to 7 for electrocatalytic hydrogen evolution.

Background

In recent years, hydrogen energy has received great attention as a green high-calorific-value energy fuel due to increasing demands for energy and environmental protection. Hydrogen production by electrolysis of water typically uses a noble metal Pt as a catalyst, mainly because Pt has a low hydrogen evolution overpotential and fast kinetics for HER. However, the problems of high cost and low stability of Pt have severely hampered large-scale commercialization of hydrogen energy production. Therefore, the development of the efficient, stable and cheap non-noble metal catalyst capable of replacing Pt is of great significance.

Many non-noble metal materials, such as transition metal sulfur compounds, boron compounds, nitrogen compounds, and metal alloys, have been extensively studied for hydrogen evolution catalysis. Scientists have experimentally and theoretically demonstrated transition metal sulfur compounds (TMDs) such as WS₂Has high catalytic activity, whereas WS₂The in-plane atomic site has low catalytic activity, limits the electron transfer capability, and leads to slow HER kinetic reaction. There are two approaches currently available to maximize the catalytic activity of WS 2. First, the WS2 metal phase ratio can be increased to improve the WS₂Intrinsic conductivity thereby enhances HER activity. 1T-WS now studied₂Due to its having a structure corresponding to 2H-WS₂Higher formation energy, direct synthesis of 1T-WS₂(especially 1T' -WS)₂The highest energy of formation, about 0.89eV, being a steady state structure) presents a significant challenge. One may remove 2H-WS from the substrate by wet chemistry or lift-off₂Obtaining WS as a 1T (1T')/2H mixed phase₂However, the metal phase synthesized by such methods is unstable in air and cannot be effectively and continuously used for HER catalysis. Second, HER catalytic activity can be improved by increasing reactive sites. By introducing metal monatomic catalysts (SACs)) Anchored in WS₂The catalytic activity of the metal catalyst can be maximally increased on the carrier, and the utilization rate of metal atoms is improved. Still someone has effectively increased WS through argon plasma etching technique₂The active specific surface area of the compound improves the number of active sites, thereby optimizing HER catalysis. However, modification of WS by RF back-sputtering₂The improvement of HER catalytic activity by films has not been reported.

Disclosure of Invention

In view of the above defects, the present invention provides a transition group metal compound hydrogen evolution thin film, which includes a substrate layer and a hydrogen evolution catalyst layer, wherein the hydrogen evolution catalyst layer is arranged on the surface of the substrate layer, and the hydrogen evolution catalyst layer is a thin film formed by one of a transition group metal sulfur compound, a transition group metal selenium compound and a transition group metal tellurium compound.

Preferably, the hydrogen evolution catalyst layer is MoS₂、WS₂、MoSe₂、WSe₂、MoTe₂And WTE₂A film made of one of the above materials.

Preferably, the substrate layer is made of metal or ceramic;

when the substrate layer is made of metal, the metal is one of V, Nb, Ta, Mo, Ni, Ti, Pd, Pt, porous stainless steel, V/Ni alloy, V/Cr alloy, V/Cu alloy, V/Fe alloy, V/Al alloy, V/Co alloy, V/Mo alloy, V/W alloy, V/Ti/Ni alloy, V/Fe/Al alloy, V/Mo/W alloy, Nb/Ti/Ni alloy, Nb/Ti/Co alloy and Nb/Mo/W alloy;

when the substrate layer is ceramic, the ceramic is one of porous alumina ceramic pieces/tubes, porous zirconia ceramic pieces/tubes and zeolite.

A radio frequency back-sputtering modification preparation method of a transition group metal compound hydrogen evolution film is characterized by comprising the following steps:

the method comprises the following steps: pretreating a substrate layer;

step two: cleaning the surface of the substrate layer by using ion beams;

step three: forming a hydrogen evolution catalyst layer on the surface of the substrate layer by adopting one of chemical vapor deposition, hydrothermal synthesis, magnetron sputtering, ion beam sputtering, electron beam evaporation, pulse deposition, molecular beam epitaxy and atomic layer deposition;

step four: and irradiating the surface of the hydrogen evolution catalyst layer to etch by utilizing a radio frequency back sputtering mode.

Preferably, in the step one, the substrate layer is ultrasonically cleaned for 5-15min by sequentially adopting acetone and absolute ethyl alcohol, the ultrasonic cleaning is repeated for 2-3 times, and then the substrate layer is washed for 1-2 minutes by using deionized water and then dried.

Preferably, in the third step, magnetron sputtering is used to form the hydrogen evolution catalyst layer on the surface of the substrate layer.

Preferably, the cleaning conditions in the second step include: the vacuum degree in the sputtering cavity is less than 10^-4Pa, substrate temperature of 25-600 deg.C, substrate negative bias of 0-300V, argon flow of 3-20sccm, working pressure of 0.2-1.0Pa, sputtering power of 0-300V, and irradiation time of 5-10 min.

The magnetron sputtering conditions of the step three comprise: the vacuum degree in the sputtering cavity is less than 10^-4Pa, the temperature of the basal layer is 25-600 ℃, the negative bias of the basal layer is 0-500V, the flow of introduced argon is 3-30sccm, the working pressure is 0.2-2.0Pa, the sputtering power is 0-300V, and the irradiation time is 5-100 min;

the conditions of the radio frequency back splash in the fourth step comprise: the vacuum degree in the sputtering cavity is less than 10^-4Pa, introducing argon gas flow of 3-70sccm, working pressure of 1.0-50Pa, sputtering power of 0-300V, and irradiation time of 0-5 min.

Preferably, the application of the transition metal compound hydrogen evolution film in electrocatalytic hydrogen evolution.

Compared with the prior art, the surface modification is carried out on the hydrogen evolution catalyst layer by adopting a radio frequency back-sputtering method, the radio frequency back-sputtering is a process method for achieving the purpose of cleaning the material which is coated, and ionized Ar plasma generated by the radio frequency back-sputtering randomly irradiates a sample to generate an etching effect to form random etching in the whole hydrogen evolution film plane, so that the catalytic activity of the hydrogen evolution film is obviously improved.

Drawings

In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and other drawings can be obtained by those skilled in the art without creative efforts.

FIG. 1 is a schematic structural view of a hydrogen evolution thin film;

FIG. 2 is a schematic view of an RF back-sputter etching modified transition-group metal sulfur compound film of the present invention;

FIG. 3 shows the etching modification WS in the second embodiment when the sputtering power is 0V and the irradiation time is 0min₂A surface topography photograph of the film;

FIG. 4 shows etching modified WS when the sputtering power is 100V and the irradiation time is 2min in the third embodiment₂A surface topography photograph of the film;

FIG. 5 shows modified etching WS in the fourth embodiment at a sputtering power of 150V and an irradiation time of 2min₂A surface topography photograph of the film;

FIG. 6 shows modified etching WS in the case of sputtering power of 200V and irradiation time of 2min according to example V₂A surface topography photograph of the film;

FIG. 7 shows modified etching WS in the sixth embodiment when the sputtering power is 150V and the irradiation time is 1min₂A surface topography photograph of the film;

FIG. 8 shows the etching modified WS in the case of the seventh embodiment when the sputtering power is 150V and the irradiation time is 3min₂A surface topography photograph of the film;

FIG. 9 shows modified WS by RF sputtering power and irradiation time according to example two-seven₂The film was subjected to a linear sweep voltammogram.

Wherein, the catalyst comprises a 1-basal layer and a 2-hydrogen evolution catalyst layer.

Detailed Description

The following is a detailed description of several preferred embodiments of the invention, but the invention is not limited to these embodiments only. The invention is intended to cover alternatives, modifications, equivalents, and alternatives that may be included within the spirit and scope of the invention. In the following description of the preferred embodiments of the present invention, specific details are set forth in order to provide a thorough understanding of the present invention, and it will be apparent to those skilled in the art that the present invention may be practiced without these specific details.

Example one

As shown in fig. 1, a transition group metal compound hydrogen evolution thin film includes a base layer and a hydrogen evolution catalytic layer, wherein the hydrogen evolution catalytic layer is arranged on the surface of the base layer, and the hydrogen evolution catalytic layer is a thin film formed by one of a transition group metal sulfur compound, a transition group metal selenium compound and a transition group metal tellurium compound.

In this embodiment, the hydrogen evolution catalyst layer is MoS₂、WS₂、MoSe₂、WSe₂、MoTe₂And WTE₂A film made of one of the above materials.

In this embodiment, the base layer is made of metal or ceramic;

when the substrate layer is made of metal, the metal is one of V, Nb, Ta, Mo, Ni, Ti, Pd, Pt, porous stainless steel, V/Ni alloy, V/Cr alloy, V/Cu alloy, V/Fe alloy, V/Al alloy, V/Co alloy, V/Mo alloy, V/W alloy, V/Ti/Ni alloy, V/Fe/Al alloy, V/Mo/W alloy, Nb/Ti/Ni alloy, Nb/Ti/Co alloy and Nb/Mo/W alloy;

when the substrate layer is ceramic, the ceramic is one of porous alumina ceramic pieces/tubes, porous zirconia ceramic pieces/tubes and zeolite.

Example two

A radio frequency back-sputtering modification preparation method of a transition group metal compound hydrogen evolution film is characterized by comprising the following steps:

the method comprises the following steps: pretreating the substrate layer 1;

step two: cleaning the surface of the substrate layer 1 by using ion beams;

step three: forming a hydrogen evolution catalyst layer 2 on the surface of the substrate layer 1 by adopting one of chemical vapor deposition, hydrothermal synthesis, magnetron sputtering, ion beam sputtering, electron beam evaporation, pulse deposition, molecular beam epitaxy and atomic layer deposition;

step four: etching is irradiated on the surface of the hydrogen evolution catalysis layer 2 by utilizing a radio frequency back sputtering mode.

In this embodiment, in step one, the substrate layer is ultrasonically cleaned with acetone and absolute ethyl alcohol sequentially for 5-15min, repeated for 2-3 times, and then rinsed with deionized water for 1-2 minutes, and then dried.

In this example, in step three, a hydrogen evolution catalytic layer was formed on the surface of the base layer by magnetron sputtering.

In this embodiment, the cleaning conditions in the second step include: the vacuum degree in the sputtering cavity is less than 10^-4Pa, substrate temperature of 25-600 deg.C, substrate negative bias of 0-300V, argon flow of 3-20sccm, working pressure of 0.2-1.0Pa, sputtering power of 0-300V, and irradiation time of 5-10 min.

The magnetron sputtering conditions of the step three comprise: the vacuum degree in the sputtering cavity is less than 10^-4Pa, the temperature of the basal layer is 25-600 ℃, the negative bias of the basal layer is 0-500V, the flow of introduced argon is 3-30sccm, the working pressure is 0.2-2.0Pa, the sputtering power is 0-300V, and the irradiation time is 5-100 min;

the conditions of the radio frequency back splash in the fourth step comprise: the vacuum degree in the sputtering cavity is less than 10^-4Pa, introducing argon gas flow of 3-70sccm, working pressure of 1.0-50Pa, sputtering power of 0V, and irradiation time of 0 min.

The resulting SEM image is shown in fig. 3.

EXAMPLE III

Referring to the preparation method of the radio frequency back sputtering modification of the second embodiment, the sputtering power in the fourth step is 100V, the irradiation time is 2min, and the rest steps and parameters are the same as those of the second embodiment.

The resulting SEM image is shown in fig. 4.

Example four

Referring to the preparation method of the radio frequency back sputtering modification of the second embodiment, the sputtering power in the fourth step is 150V, the irradiation time is 2min, and the rest steps and parameters are the same as those in the second embodiment.

The resulting SEM image is shown in fig. 5.

EXAMPLE five

Referring to the preparation method of the radio frequency back sputtering modification of the second embodiment, the sputtering power in the fourth step is 200V, the irradiation time is 2min, and the rest steps and parameters are the same as those of the second embodiment.

The resulting SEM image is shown in fig. 6.

EXAMPLE six

Referring to the preparation method of the radio frequency back sputtering modification of the second embodiment, the sputtering power in the fourth step is 150V, the irradiation time is 1min, and the rest steps and parameters are the same as those in the second embodiment.

The resulting SEM image is shown in fig. 7.

EXAMPLE seven

Referring to the preparation method of the radio frequency back sputtering modification of the second embodiment, the sputtering power in the fourth step is 150V, the irradiation time is 3min, and the rest steps and parameters are the same as those in the second embodiment.

The obtained SEM image is shown in fig. 8.

FIGS. 3-8 show the preparation of WS under different sputtering powers and irradiation times during RF back-sputtering₂SEM image of thin film. As can be seen from FIG. 3, WS has not been modified₂The surface of the film has a plurality of branched worm-like tissues, and the branches are nano structures with uniform and fine tissues. As can be seen from FIGS. 4-6, when the irradiation time is 2min, the tissue changes from fine to porous and then becomes coarse as the sputtering power increases. When the power is 100W, the tissues are obviously thinned, the sizes of all the tissues are nano-scale, and the integrity of the film is not damaged, because S, W atoms on the surface of the film obtain the energy of surface migration under the action of Ar plasma, the surface tissues of the film are more uniform and fine, and more active sites can be exposed; when the power is increased to 150W, the surface tissue is still fine, the whole film is complete, and partial tissue is damaged, because the power is increased, the kinetic energy of Ar plasma is also increased, so that the tissue is thinned, individual tissue is damaged, and the active sites are more exposed; when the power is further increased to 200W, the tissue on the surface of the film is damaged at multiple positions, the tissue is agglomerated, the original form is lost, and the size is thickened because the Ar plasma irradiates the surface of the film when the power is too highAt high intensity, the original tissue is destroyed, S, W obtains excessive energy, and the tissue is coarse. From fig. 5, 7 and 8, it can be seen that when the sputtering powers are all 150W, the tissue changes from fine to porous and then becomes coarse with the increase of the irradiation time, similar to the result when the sputtering powers are changed separately.

WS modified by using electrochemical devices with different radio frequency sputtering powers and irradiation times in the second to the seventh embodiments₂The polarization curve obtained by subjecting the film to the linear sweep voltammetry test is shown in FIG. 9, from which it can be seen that the hydrogen evolution catalytic activity is highest when the sputtering power is 150W and the irradiation time is 2min, and that the overpotential is 170mV at a current density of 10mA/cm 2.

Compared with the prior art, the WS is sputtered by radio frequency for the first time₂The film is subjected to surface modification, radio frequency back sputtering is a process method for achieving the purpose of cleaning the material after film plating, ionized Ar plasma generated by radio frequency back sputtering randomly irradiates a sample to generate an etching effect, random etching in the whole hydrogen evolution film plane is formed, and the catalytic activity of the hydrogen evolution film is obviously improved.

The present embodiment is only for explaining the present invention, and it is not limited to the present invention, and those skilled in the art can make modifications of the present embodiment without inventive contribution as needed after reading the present specification, but all of them are protected by patent law within the scope of the claims of the present invention.