KR20200068906A - Hydrogen-generating catalyst and preparing method thereof - Google Patents

Abstract

The present application relates to a catalyst for generating hydrogen, comprising transition metal chalcogenides formed on a transition metal, wherein the transition metal chalcogenides are patterned. Since platinum is not used in the present invention, it is possible to reduce the cost of a hydrogen production process.

Description

Hydrogen generating catalyst and method for manufacturing the same{HYDROGEN-GENERATING CATALYST AND PREPARING METHOD THEREOF}

The present application relates to a catalyst for generating hydrogen and a method for producing the same, and more particularly, to a catalyst for generating electrochemical hydrogen and a method for producing the same.

In modern times, with the development of industrial technology, the standard of living is continuously improving, while the problem of environmental pollution and resource depletion is getting serious due to the rapid increase in energy use. In order to solve the problem of environmental pollution and resource depletion, countries are focusing on the development of clean fuels. In particular, the development of clean alternative energy using hydrogen as an energy source has attracted great interest.

The reason is that hydrogen is one of the most abundant resources in the earth, and it reacts with oxygen to generate large energy while generating only water as a by-product, thereby simultaneously solving not only the problem of resource depletion but also environmental pollution, and also high energy density per weight. This is because it has the advantage of easy conversion to heat and electrochemical energy. In other words, hydrogen can be the only alternative that can overcome the depletion of non-existent resources, global warming and environmental pollution.

In the method of supplying hydrogen by a catalyst for generating hydrogen, hydrogen is generated by reacting a catalyst for generating hydrogen with alkali water or ammonia water such as water, acid solution, NaOH, KOH, and the like. Although the most representative catalyst for hydrogen generation is platinum, research is being actively conducted to develop a catalyst that can replace platinum due to the high price of the material.

On the other hand, block copolymers in which two or more chemically distinct polymer chains are connected by covalent bonds are separated into regular microphases due to their self-assembly. The microphase separation phenomenon of these block copolymers is generally described according to the volume fraction (f), molecular weight (N), and the flow-Huggins interaction parameter (χ) between the constituent components, 10 nm to 100 nm Forms various nano structures or domains such as spheres, cylinders, gyroids, and lamelae having the size of.

The self-assembly properties of block copolymers are in the spotlight for the production of patterns in nanostructures, which require relatively low cost and simple manufacturing process for pattern production using block copolymers compared to conventional photo lithography methods. It is because. The existing top-down method of photolithography shows fundamental limitations such as light dispersion and light source limitation due to the characteristics of the technology, thus reaching the limit of manufacturing nanometer scale fine patterns. As an alternative to overcome this, the use of materials showing self-assembly properties is emerging, and among them, self-assembly properties of block copolymers in the thin film state are currently receiving the greatest attention.

Korean Patent Publication No. 10-1847772, which is the background technology of the present application, discloses a photocatalyst for decomposing water and a method for producing hydrogen using the same. Specifically, the registered patent discloses a structure including a tantalum nitride doped with a transition metal and a coating layer surrounding the tantalum nitride and including a conductive polymer.

The present application is to solve the problems of the above-described prior art, it is an object to provide a catalyst for generating hydrogen and a method for producing the same.

However, the technical problems to be achieved by the embodiments of the present application are not limited to the technical problems as described above, and other technical problems may exist.

As a technical means for achieving the above technical problem, the first aspect of the present application includes a transition metal chalcogen compound formed on a transition metal, and the transition metal chalcogen compound is patterned, a catalyst for hydrogen generation Provides

According to one embodiment of the present application, the transition metal may be the same pattern as the transition metal chalcogenide compound, but is not limited thereto.

According to the exemplary embodiment of the present application, the patterning may include an uneven structure, but is not limited thereto.

According to the exemplary embodiment of the present application, the uneven structure may have a pitch of 10 nm to 50 nm, but is not limited thereto.

According to one embodiment of the present application, the transition metal is a transition metal selected from the group consisting of molybdenum (Mo), tungsten (W), rhenium (Re), tantalum (Ta), titanium (Ti), and combinations thereof. It may be to include, but is not limited thereto.

According to one embodiment of the present application, the transition metal chalcogenide compound is MoS ₂ , MoSe ₂ , MoTe ₂ , WS ₂ , WSe ₂ , WTe ₂ , ReS ₂ , ReSe ₂ , ReTe ₂ , TaS ₂ , TaSe ₂ , TaTe ₂ , TiS ₂ , TiSe ₂ , TiTe ₂ , and combinations thereof, but may include materials selected from the group, but are not limited thereto.

The second aspect of the present application comprises the steps of depositing a transition metal on the substrate using a physical vapor deposition method; Depositing a transition metal chalcogen compound using a chemical vapor deposition method by providing a chalcogen source on the transition metal; Depositing a protective layer on the transition metal chalcogenide compound; Laminating a block copolymer on the protective layer; The block copolymer is self-assembled (self-assembly) to form a pattern having a porous structure; Patterning the protective layer according to the pattern; And patterning the transition metal chalcogen compound using the patterned protective layer as a mask.

According to the exemplary embodiment of the present application, the transition metal may be patterned by patterning the transition metal chalcogen compound, but is not limited thereto.

According to one embodiment of the present application, the block copolymer may be self-assembled by heat treatment or light treatment, but is not limited thereto.

According to one embodiment of the present application, the block copolymer may be self-assembled to control the size of the porous structure in a step of forming a pattern having a porous structure, but is not limited thereto.

According to one embodiment of the present application, the block copolymer is PS-b-PMMA, PS-r-PMMA, PS-b-PBMA, PS-b-P2VP, PS-b-P4VP, PS-b-PB, PEO -b-PIP, PB-b-PEO, and may include a material selected from the group consisting of, but is not limited to.

According to one embodiment of the present application, the block copolymer may have a thickness of 10 nm to 60 nm, but is not limited thereto.

According to the exemplary embodiment of the present application, the chalcogen source may include a material selected from the group consisting of sulfur (S), tellurium (Te), selenium (Se), and combinations thereof, but is not limited thereto. It is not.

According to one embodiment of the present application, the chalcogen source may be in a solid state or a gas state, but is not limited thereto.

According to one embodiment of the present application, the physical vapor deposition method may be performed by a method selected from the group consisting of a sputtering method, an electron beam deposition method, a thermal deposition method, an ion cluster beam, a pulse laser deposition method, and combinations thereof. However, it is not limited thereto.

According to one embodiment of the present application, the protective layer is SiO ₂ , Al ₂ O ₃ , ZrO ₂ , Si ₃ N ₄ , SiC, AlN, Fe ₂ O ₃ , ZnO, BN, Si ₃ N ₄ , and combinations thereof It may be to include a ceramic selected from the group consisting of, but is not limited thereto.

According to the exemplary embodiment of the present application, the protective layer may be induced to stack the block copolymer on the transition metal chalcogen compound using a ceramic having a hydrophilic functional group, but is not limited thereto.

According to the exemplary embodiment of the present application, the patterning includes reactive ion etching (RIE), reactive plasma etching (RPE), sputter etching, vapor phase etching, And it may be performed by a method selected from the group consisting of these, but is not limited thereto.

The above-described problem solving means are merely exemplary and should not be construed as limiting the present application. In addition to the exemplary embodiments described above, additional embodiments may exist in the drawings and detailed description of the invention.

According to the above-described problem solving means of the present application, the catalyst for hydrogen generation of the present application can maximize the area of the edge having high catalytic activity by forming a pattern of the uneven structure on the transition metal chalcogen compound using a block copolymer. . As the reaction area of the transition metal chalcogen compound increases when hydrogen is generated, excellent catalytic properties such as small tapel slope, small starting potential, high current exchange density, and high stability can be expected.

In addition, the method for producing a catalyst for hydrogen generation of the present application first, deposits a transition metal using a physical vapor deposition method, and then synthesizes a transition metal chalcogen compound using a chemical vapor deposition method. Compounds can be grown. Furthermore, since the thickness of the transition metal chalcogen compound is determined according to the thickness of the transition metal that is first deposited, the thickness of the transition metal chalcogen compound can be easily adjusted.

On the other hand, the method for producing a catalyst for generating hydrogen according to the present application can reduce the cost of a hydrogen production process by using a transition metal chalcogen compound instead of an expensive platinum catalyst mainly used in the past.

1 is a cross-sectional view of a catalyst for generating hydrogen according to an embodiment of the present application.
2 is a flowchart of a method for producing a catalyst for hydrogen generation according to an embodiment of the present application.
3 is a schematic diagram of a method for producing a catalyst for generating hydrogen according to an embodiment of the present application.
4 is a schematic diagram of water decomposition using a catalyst for generating hydrogen according to an embodiment of the present application.
5 is an experimental graph comparing the performance of a catalyst for hydrogen generation according to an example and a comparative example of the present application.
6 is an experimental graph comparing the performance of a catalyst for hydrogen generation according to an example and a comparative example of the present application.

Hereinafter, embodiments of the present application will be described in detail with reference to the accompanying drawings so that those skilled in the art to which the present application pertains may easily practice. However, the present application may be implemented in various different forms and is not limited to the embodiments described herein. In addition, in order to clearly describe the present application in the drawings, parts irrelevant to the description are omitted, and like reference numerals are assigned to similar parts throughout the specification.

Throughout this specification, when a part is "connected" to another part, this includes not only "directly connected" but also "electrically connected" with another element in between. do.

Throughout the present specification, when a member is positioned on another member “on”, “on the top”, “top”, “bottom”, “bottom”, “bottom”, this means that one member is attached to another member. This includes cases where there is another member between the two members as well as when in contact.

Throughout the present specification, when a part “includes” a certain component, it means that the component may further include other components, not to exclude other components, unless specifically stated to the contrary.

Throughout this specification, when a part “includes” a certain component, it means that the component may further include other components, not to exclude other components, unless otherwise stated.

As used herein, the terms “about”, “substantially”, and the like are used in or near the numerical values when manufacturing and substance tolerances unique to the stated meanings are presented, to aid understanding of the present application Hazards are used to prevent unreasonable abuse by unscrupulous infringers of the disclosures that are either accurate or absolute. In addition, throughout the present specification, "step of" or "step of" does not mean "step for".

Throughout the present specification, the term “combination of these” included in the expression of the marki form means one or more mixtures or combinations selected from the group consisting of the components described in the expression of the marki form, the component. It means to include one or more selected from the group consisting of.

Throughout this specification, the description of “A and/or B” means “A or B, or A and B”.

Throughout the present specification, "concave-convex structure" means concave and convex.

Hereinafter, a catalyst for generating hydrogen and a method for manufacturing the same will be described in detail with reference to embodiments and examples and drawings. However, the present application is not limited to these embodiments and examples and drawings.

As a technical means for achieving the above technical problem, the first aspect of the present application includes a transition metal chalcogen compound formed on a transition metal, and the transition metal chalcogen compound is patterned, a catalyst for hydrogen generation Provides

1 is a cross-sectional view of a catalyst for generating hydrogen according to an embodiment of the present application.

Referring to FIG. 1, the catalyst for hydrogen generation according to an embodiment of the present application 100 includes a transition metal 120 and a transition metal chalcogen compound 130.

According to one embodiment of the present application, the transition metal 120 may be the same pattern as the transition metal chalcogen compound 130, but is not limited thereto. The transition metal 120 may form the same pattern as the transition metal chalcogen compound 130 is patterned.

According to the exemplary embodiment of the present application, the patterning may include an uneven structure, but is not limited thereto. Specifically, the uneven structure may have a cylinder shape.

The present inventors confirmed that the transition metal chalcogen compound has superior catalytic activity at the edge than the mineral surface through DFT (Density Functional Theory) calculation and experiment. By using this, the transition metal chalcogen compound 130 may be patterned to include an uneven structure to increase the area of the edge of the transition metal chalcogen compound 130 having high catalytic activity. As a result, when hydrogen is generated using the catalyst 100 for generating hydrogen, the reaction area of the transition metal chalcogen compound 130 can be increased to have a small tapel slope and a small starting potential, and a high current exchange density. By bringing a large amount of electrons to a small potential, hydrogen generation can be increased.

According to the exemplary embodiment of the present application, the uneven structure may have a pitch of 10 nm to 50 nm, but is not limited thereto. For example, the uneven structure may have a pitch of 10 nm to 50 nm, 10 nm to 40 nm, 10 nm to 30 nm, 20 nm to 50 nm, 20 nm to 40 nm, 20 nm to 30 nm, , But is not limited thereto.

According to one embodiment of the present application, the transition metal 120 is in the group consisting of molybdenum (Mo), tungsten (W), rhenium (Re), tantalum (Ta), titanium (Ti), and combinations thereof. It may be to include a selected transition metal, preferably molybdenum, but is not limited thereto.

According to one embodiment of the present application, the transition metal chalcogenide compound 130 is MoS ₂ , MoSe ₂ , MoTe ₂ , WS ₂ , WSe ₂ , WTe ₂ , ReS ₂ , ReSe ₂ , ReTe ₂ , TaS ₂ , TaSe ₂ , TaTe ₂ , TiS ₂ , TiSe ₂ , TiTe ₂ , and combinations thereof, and may include a material selected from the group, preferably MoS ₂ , but is not limited thereto.

The second aspect of the present application comprises the steps of depositing the transition metal 120 on the substrate 110 using a physical vapor deposition method; Depositing a transition metal chalcogen compound 130 using a chemical vapor deposition method by providing a chalcogen source on the transition metal 120; Depositing a protective layer 140 on the transition metal chalcogen compound 130; Depositing a block copolymer (150) on the protective layer (140); The block copolymer 150 is self-assembled (self-assembly) to form a pattern having a porous structure; Patterning the protective layer 140 according to the pattern; And patterning the transition metal chalcogen compound 130 using the patterned protective layer 140 as a mask.

2 is a flowchart of a method for producing a catalyst for generating hydrogen according to an embodiment of the present application, and FIG. 3 is a schematic diagram of a method for producing a catalyst for generating hydrogen according to an embodiment of the present application.

Hereinafter, a method of manufacturing the catalyst for generating hydrogen will be described with reference to FIGS. 2 to 3.

First, the transition metal 120 is deposited on the substrate 110 using a physical vapor deposition method (S100).

According to one embodiment of the present application, the physical vapor deposition method may be performed by a method selected from the group consisting of a sputtering method, an electron beam deposition method, a thermal deposition method, an ion cluster beam, a pulse laser deposition method, and combinations thereof. And, it may be preferably performed by a sputtering method, but is not limited thereto.

Physical vapor deposition is a method of depositing a material such as a thin film to be deposited on a substrate through evaporation or sputtering in vacuum.

The sputtering method is a method of accelerating a gas such as argon ionized by plasma at a relatively low vacuum level to collide with a target, and ejecting atoms of the target to form a thin film on a substrate. The sputtering method is characterized by having excellent deposition ability, ability to maintain a complex alloy, and excellent deposition ability of a heat-resistant metal at high temperatures.

Subsequently, a chalcogen source is provided on the transition metal 120 to deposit the transition metal chalcogen compound 130 using a chemical vapor deposition method (S200).

The chemical vapor deposition method is a method of supplying a raw material in powder or gaseous form on a substrate, and forming a thin film on the surface of the substrate by chemical reactions such as gas phase or thermal decomposition, photolysis, redox reaction, substitution on the substrate surface.

According to one embodiment of the present application, the chalcogen source may include a material selected from the group consisting of sulfur (S), tellurium (Te), selenium (Se), and combinations thereof, preferably It may be sulfur, but is not limited thereto.

According to one embodiment of the present application, the chalcogen source may be in a solid state or a gas state, but is not limited thereto.

The chemical vapor deposition method may be performed by placing the substrate 110 on which the transition metal 120 is deposited in a chamber having a temperature of 500°C to 1000°C and a pressure of 200 mTorr to 800 mTorr for 1 hour, but is not limited thereto. It is not.

For example, the chamber is 500 ℃ to 1000 ℃, 500 ℃ to 950 ℃, 500 ℃ to 900 ℃, 500 ℃ to 850 ℃, 500 ℃ to 800 ℃, 500 ℃ to 750 ℃, 550 ℃ to 1000 ℃, 550 ℃ to 950 ℃, 550 ℃ to 900 ℃, 550 ℃ to 850 ℃, 550 ℃ to 800 ℃, 550 ℃ to 750 ℃, 600 ℃ to 1000 ℃, 600 ℃ to 950 ℃, 600 ℃ to 900 ℃, 600 ℃ to 850℃, 600℃ to 800℃, 600℃ to 750℃, 650℃ to 1000℃, 650℃ to 950℃, 650℃ to 900℃, 650℃ to 850℃, 650℃ to 800℃, 650℃ to 750℃ , 700℃ to 1000℃, 700℃ to 950℃, 700℃ to 900℃, 700℃ to 850℃, 700℃ to 800℃, 700℃ to 750℃, but is not limited thereto. .

In addition, for example, the chamber is 200 mTorr to 800 mTorr, 200 mTorr to 750 mTorr, 200 mTorr to 700 mTorr, 200 mTorr to 650 mTorr, 200 mTorr to 600 mTorr, 200 mTorr to 550 mTorr, 200 mTorr to 500 mTorr , 250 mTorr to 800 mTorr, 250 mTorr to 750 mTorr, 250 mTorr to 700 mTorr, 250 mTorr to 650 mTorr, 250 mTorr to 600 mTorr, 250 mTorr to 550 mTorr, 250 mTorr to 500 mTorr, 300 mTorr to 800 mTorr, 300 mTorr to 750 mTorr, 300 mTorr to 700 mTorr, 300 mTorr to 650 mTorr, 300 mTorr to 600 mTorr, 300 mTorr to 550 mTorr, 300 mTorr to 500 mTorr, 350 mTorr to 800 mTorr, 350 mTorr to 750 mTorr, 350 mTorr to 700 mTorr, 350 mTorr to 650 mTorr, 350 mTorr to 600 mTorr, 350 mTorr to 550 mTorr, 350 mTorr to 500 mTorr, 400 mTorr to 800 mTorr, 400 mTorr to 750 mTorr, 400 mTorr to 700 mTorr, 400 mTorr to 650 mTorr , 400 mTorr to 600 mTorr, 400 mTorr to 550 mTorr, 400 mTorr to 500 mTorr, 450 mTorr to 800 mTorr, 450 mTorr to 750 mTorr, 450 mTorr to 700 mTorr, 450 mTorr to 650 mTorr, 450 mTorr to 600 mTorr, 450 mTorr to 550 mTorr , It may be performed at a pressure of 450 mTorr to 500 mTorr, but is not limited thereto.

The conventional method for producing a catalyst for hydrogen generation has a problem in that it is difficult to grow at a high temperature of 200° C. or higher because a transition metal chalcogen compound is deposited on a textile polymer fiber using an atomic layer deposition method. However, since the present invention synthesizes the transition metal chalcogen compound 130 using a chemical vapor deposition method after first depositing the transition metal 120 by physical vapor deposition, the uniform transition metal chalcogen compound 130 is irrespective of temperature. ) Can be synthesized in a large area.

In addition, since the thickness of the transition metal chalcogen compound 130 is determined according to the thickness of the transition metal 120 deposited by a physical vapor deposition method, the thickness of the transition metal chalcogen compound 130 can be easily adjusted. .

The transition metal chalcogen compound is drawing attention as a two-dimensional material that can replace graphene. Since the transition metal chalcogen compound principally only has a two-dimensional interaction with constituent atoms, the transport of carriers in the transition metal chalcogen compound exhibits a ballistic transport pattern, unlike a typical thin film or bulk, from which Mobility, high speed, and low power characteristics may be implemented.

In particular, MoS ₂ is a typical transition metal chalcogen compound, and has a sandwich structure in which molybdenum (Mo) is interposed between sulfur (S). MoS ₂ is layered through a very strong covalent bond between atoms, while each layer has a two-dimensional layered structure with weak van der Waals bonds.

Subsequently, a protective layer 140 is deposited on the transition metal chalcogen compound 130 (S300).

According to one embodiment of the present application, the protective layer 140 is SiO ₂ , Al ₂ O ₃ , ZrO ₂ , Si ₃ N ₄ , SiC, AlN, Fe ₂ O ₃ , ZnO, BN, Si ₃ N ₄ , and It may be to include a ceramic selected from the group consisting of these combinations, and preferably SiO ₂ , Al ₂ O ₃ , but is not limited thereto.

According to the exemplary embodiment of the present application, the protective layer 140 may be to induce the block copolymer 150 to be stacked on the transition metal chalcogen compound 130 using a ceramic having a hydrophilic functional group. However, it is not limited thereto.

Since there are almost no dangling bonds on the surface of the transition metal chalcogen compound, it is difficult to directly stack the block copolymer. In order to solve this problem, the protective layer 140 may include a ceramic containing a hydrophilic functional group that induces the block copolymer 150 to be stacked on the transition metal chalcogen compound 130. In addition, the protective layer 140 serves to protect the transition metal chalcogen compound 130 in the step of patterning the transition metal chalcogen compound 130.

Subsequently, a block copolymer 150 is stacked on the protective layer 140 (S400).

According to one embodiment of the present application, the block copolymer 150 is PS-b-PMMA, PS-r-PMMA, PS-b-PBMA, PS-b-P2VP, PS-b-P4VP, PS-b- PB, PEO-b-PIP, PB-b-PEO, and may be one containing a material selected from the group consisting of combinations, preferably comprising PS-b-PMMA, PS-r-PMMA However, it is not limited thereto.

Specifically, in order to form the block copolymer 150 uniformly, PS-r-PMMA may be treated first on the surface of the protective layer 140 and then PS-b-PMMA.

According to one embodiment of the present application, the block copolymer 150 may have a thickness of 10 nm to 60 nm, but is not limited thereto.

For example, the block copolymer 150 is 10 nm to 60 nm, 10 nm to 55 nm, 10 nm to 50 nm, 10 nm to 45 nm, 10 nm to 40 nm, 15 nm to 60 nm, 15 nm To 55 nm, 15 nm to 50 nm, 15 nm to 45 nm, 15 nm to 40 nm, 20 nm to 60 nm, 20 nm to 55 nm, 20 nm to 50 nm, 20 nm to 45 nm, 20 nm to 40 nm, 25 nm to 60 nm, 25 nm to 55 nm, 25 nm to 50 nm, 25 nm to 45 nm, 25 nm to 40 nm, 30 nm to 60 nm, 30 nm to 55 nm, 30 nm to 50 nm, 30 nm to 45 nm, may have a thickness of 30 nm to 40 nm, but is not limited thereto.

Subsequently, the block copolymer 150 is self-assembled to form a pattern having a porous structure (S500).

Self-assembly is a property in which molecules form a specific nanostructure by themselves, and using a block copolymer self-assembly property can effectively produce a regular pattern of nanometer size.

According to one embodiment of the present application, the block copolymer 150 may be self-assembled by heat treatment or light treatment, but is not limited thereto.

According to one embodiment of the present application, the block copolymer 150 may be self-assembled to control the size of the porous structure in a step of forming a pattern having a porous structure, but is not limited thereto. Specifically, adjusting the size of the porous structure may be performed by oxygen plasma gas etching.

The pattern may include an uneven structure, but is not limited thereto. Specifically, the uneven structure may have a cylinder shape.

The size of the porous structure may be 10 nm to 50 nm, but is not limited thereto. For example, the porous structure may have a size of 10 nm to 50 nm, 10 nm to 40 nm, 10 nm to 30 nm, 20 nm to 50 nm, 20 nm to 40 nm, 20 nm to 30 nm, , But is not limited thereto.

Subsequently, the protective layer 140 is patterned according to the pattern (S600).

According to the exemplary embodiment of the present application, the patterning includes reactive ion etching (RIE), reactive plasma etching (RPE), sputter etching, vapor phase etching, And it may be carried out by a method selected from the group consisting of a combination of these, preferably may be performed by reactive ion etching, but is not limited thereto.

Subsequently, the transition metal chalcogen compound 130 is patterned using the patterned protective layer 140 as a mask (S700).

The present inventors confirmed that the transition metal chalcogen compound has superior catalytic activity at the edge than the mineral surface through DFT (Density Functional Theory) calculation and experiment. By using this, the transition metal chalcogen compound 130 may be patterned to include an uneven structure to increase the edge of the transition metal chalcogen compound 130 having high catalytic activity. As a result, when hydrogen is generated using the catalyst 100 for generating hydrogen, the reaction area of the transition metal chalcogen compound 130 can be increased to have a small tapel slope and a small starting potential, and a high current exchange density. By bringing a large amount of electrons to a small potential, hydrogen generation can be increased.

According to the exemplary embodiment of the present application, the transition metal 120 may be patterned by patterning the transition metal chalcogen compound 130, but is not limited thereto.

The patterning is a group consisting of Reactive Ion Etching (RIE), Reactive Plasma Etching (RPE), Sputter Etching, Vapor Phase Etching, and combinations thereof. It may be performed by a method selected from, and may be preferably performed by reactive ion etching, but is not limited thereto.

The patterning may include forming a pattern including an uneven structure on the transition metal chalcogen compound 130 by the patterning. Specifically, the uneven structure may have a cylinder shape.

The uneven structure may have a pitch of 10 nm to 50 nm, but is not limited thereto. For example, the uneven structure may have a pitch of 10 nm to 50 nm, 10 nm to 40 nm, 10 nm to 30 nm, 20 nm to 50 nm, 20 nm to 40 nm, 20 nm to 30 nm, , But is not limited thereto.

The present invention will be described in more detail through the following examples, but the following examples are for illustrative purposes only and are not intended to limit the scope of the present application.

[Example]

First, molybdenum (Mo) was deposited on a Si substrate by sputtering deposition. At this time, in the deposition step, DC power was 80 W, the substrate temperature was 500°C, the process pressure was 7 mTorr, the amount of Ar gas was 65 sccm, and the process time was 15 seconds. The deposited Mo had a thickness of 10 nm. Next, the substrate on which Mo was deposited was placed in a CVD chamber to form MoS ₂ . At this time, the forming step was performed under conditions that the chamber temperature was 750°C, the pressure was 500 mTorr, and the reaction time was 1 hour. At this time, Mo and MoS ₂ may be formed on the substrate together.

Then, SiO ₂ on the MoS ₂ Oxide (oxide) material containing a structure of 10 nm as a protective layer, this method includes an electron beam deposition method (e-beam evaporation), an atomic layer deposition method (atomic layer deposition; ALD). In order to pattern the transition metal calgogen compound, a film having micropores having a diameter of several nm was first formed. The random copolymer material was applied to the surface at 3000 rpm 30 seconds through a spin-coating method, and immediately afterwards, heat treatment was performed at 230°C for 2 hours. Afterwards, it was immersed in a toluene solution for 3 minutes. Block copolymer material was applied in the form of a film on the top of the random copolymer at 3000 rpm 30 seconds through a spin-coating method and then heat treated at 230° C. for 2 hours. Soaked in a toluene solution for 3 minutes. When the photoreaction was induced for 30 minutes through a UV lamp having a wavelength of 265 nm, a film with fine pores of several nanometers in diameter was formed.

Subsequently, the sacrificial layer and the transition metal chalcogen compound were etched and patterned using an etch-inducing gas containing SF ₆ or BCl ₃ gas.

[Comparative example]

As a comparative example, a catalyst for generating hydrogen using Pt was used instead of MoS ₂ .

[Experimental Example]

4 is a schematic diagram of water decomposition using a catalyst for generating hydrogen according to an embodiment of the present application.

4, the reference electrode is Ag / AgCl, the counter electrode is a platinum wire (Pt wire), the working electrode uses a catalyst for hydrogen generation according to an embodiment of the present application, and the electrode of the working electrode is a silicon wafer. The electrolyte is an acid solvent, and H ₂ SO ₄ is usually used.

5 is an experimental graph comparing the performance of a catalyst for hydrogen generation according to an example and a comparative example of the present application.

Referring to FIG. 5, it can be seen that the catalyst for hydrogen generation according to the above example shows a close starting potential and a relatively low tapel slope with the catalyst for hydrogen generation according to the comparative example. This shows that the performance of the catalyst for hydrogen generation according to the Examples is sufficiently available.

6 is an experimental graph comparing the performance of a catalyst for hydrogen generation according to an example and a comparative example of the present application.

Referring to Figure 6, it can be seen that the catalyst for hydrogen generation according to the embodiment has a faster slope than the catalyst for hydrogen generation according to the comparative example. This shows that the performance of the catalyst for hydrogen generation according to the Example is significantly improved compared to that of the comparative example.

The above description of the present application is for illustrative purposes, and those skilled in the art to which the present application pertains will understand that it is possible to easily modify to other specific forms without changing the technical spirit or essential features of the present application. Therefore, it should be understood that the embodiments described above are illustrative in all respects and not restrictive. For example, each component described as a single type may be implemented in a distributed manner, and similarly, components described as distributed may be implemented in a combined form.

The scope of the present application is indicated by the claims below, rather than the detailed description, and it should be interpreted that all modifications or variations derived from the meaning and scope of the claims and equivalent concepts thereof are included in the scope of the present application.

100: catalyst for hydrogen generation
110: substrate
120: transition metal
130: transition metal chalcogenide compound
140: protective layer
150: block copolymer

Claims (18)

A transition metal chalcogen compound formed on a transition metal
Including,
The transition metal chalcogenide compound is patterned, a catalyst for generating hydrogen.
According to claim 1,
The transition metal is the same patterned as the transition metal chalcogen compound, a catalyst for hydrogen generation.
According to claim 1,
The patterning is to include a concavo-convex structure, a catalyst for hydrogen generation.
The method of claim 3,
The uneven structure has a pitch of 10 nm to 50 nm, the catalyst for hydrogen generation.
According to claim 1,
The transition metal includes a transition metal selected from the group consisting of molybdenum (Mo), tungsten (W), rhenium (Re), tantalum (Ta), titanium (Ti), and combinations thereof. Dragon catalyst.
According to claim 1,
The transition metal chalcogenide compound is MoS ₂ , MoSe ₂ , MoTe ₂ , WS ₂ , WSe ₂ , WTe ₂ , ReS ₂ , ReSe ₂ , ReTe ₂ , TaS ₂ , TaSe ₂ , TaTe ₂ , TiS ₂ , TiSe ₂ , TiTe ₂ , and a material selected from the group consisting of combinations thereof.
Depositing a transition metal on the substrate using a physical vapor deposition method;
Depositing a transition metal chalcogen compound using a chemical vapor deposition method by providing a chalcogen source on the transition metal;
Depositing a protective layer on the transition metal chalcogenide compound;
Laminating a block copolymer on the protective layer;
The block copolymer is self-assembled (self-assembly) to form a pattern having a porous structure;
Patterning the protective layer according to the pattern; And
Patterning the transition metal chalcogenide compound using the patterned protective layer as a mask
A method for producing a catalyst for generating hydrogen, comprising a.
The method of claim 7,
Patterning the transition metal by the step of patterning the transition metal chalcogenide compound,
Method for producing catalyst for hydrogen generation.
The method of claim 7,
The block copolymer is self-assembled by heat treatment or light treatment, a method for producing a catalyst for hydrogen generation.
The method of claim 7,
A method for producing a catalyst for generating hydrogen, comprising adjusting the size of the porous structure in a step in which the block copolymer is self-assembled to form a pattern having a porous structure.
The method of claim 7,
The block copolymer is PS-b-PMMA, PS-r-PMMA, PS-b-PBMA, PS-b-P2VP, PS-b-P4VP, PS-b-PB, PEO-b-PIP, PB-b -PEO, and a material selected from the group consisting of combinations, the method for producing a catalyst for hydrogen generation.
The method of claim 7,
The block copolymer having a thickness of 10 nm to 60 nm, the method for producing a catalyst for generating hydrogen.
The method of claim 7,
The chalcogen source comprises a material selected from the group consisting of sulfur (S), tellurium (Te), selenium (Se), and combinations thereof, a method for producing a catalyst for hydrogen generation.
The method of claim 7,
The chalcogen source is a solid state or a gaseous state, a method for producing a catalyst for hydrogen generation.
The method of claim 7,
The physical vapor deposition method is performed by a method selected from the group consisting of a sputtering method, an electron beam deposition method, a thermal deposition method, an ion cluster beam, a pulse laser deposition method, and combinations thereof, and a method for producing a catalyst for hydrogen generation .
The method of claim 7,
The protective layer is selected from the group consisting of SiO ₂ , Al ₂ O ₃ , ZrO ₂ , Si ₃ N ₄ , SiC, AlN, Fe ₂ O ₃ , ZnO, BN, Si ₃ N ₄ , and combinations thereof. The method for producing a catalyst for generating hydrogen, which includes.
The method of claim 16,
The protective layer is a method for producing a catalyst for generating hydrogen, which is induced to stack the block copolymer on the transition metal chalcogenide compound using a hydrophilic functional ceramic.
The method of claim 7,
The patterning is a group consisting of Reactive Ion Etching (RIE), Reactive Plasma Etching (RPE), Sputter Etching, Vapor Phase Etching, and combinations thereof. It is carried out by a method selected from the method for producing a catalyst for hydrogen generation.

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