KR20220039356A - Electrocatalyst for hydrogen generation reaction comprising nitrogen-doped carbonized polydopamine structure - Google Patents

Abstract

One embodiment of the present invention provides an electrocatalyst for a hydrogen generation reaction which comprises a nitrogen-doped polydopamine carbide nanocarbon structure. The polydopamine carbide nano carbon structure is calcined under a nitrogen atmosphere using polydopamine as a precursor to be nitrogen-doped and carbonized. According to one embodiment of the present invention, it is possible to provide the efficient electrocatalyst for a hydrogen generation reaction which can be manufactured through a simple process and has high electrochemical performance.

Description

Electrocatalyst for hydrogen generation reaction comprising nitrogen-doped carbonized polydopamine structure

The present invention relates to an electrocatalyst for hydrogen generation reaction, and more particularly, to an electrocatalyst for hydrogen generation reaction comprising polydopamine doped with nitrogen and carbonized polydopamine by calcining in a nitrogen atmosphere using polydopamine as a precursor.

Due to limited fossil fuels, rising oil prices, and global warming, the world is actively developing eco-friendly energy. Among them, if hydrogen, which uses water as a raw material, is used as an energy source, not only the environmental problem of fossil fuels but also the energy depletion problem can be solved. 'Electrolysis of water' is the most well-known technology for producing hydrogen from non-fossil fuels, and catalysts that lower the overvoltage for efficient hydrogen production for this hydrogen-evolution reaction (HER) have been actively developed. is losing

Currently, as a catalyst for HER, in addition to platinum (Pt), a transition metal sulfide, carbide, phosphide, boride, etc. are widely used. However, platinum belongs to a precious metal and there is a large demand for it, so it is expensive to commercialize, and the low stability of platinum also remains an area that needs improvement.

In order to solve this problem, recently, carbon materials doped with non-metal heteroatoms have been studied as electrocatalysts for water decomposition. It is noteworthy that carbon-based catalysts can be engineered to exhibit specific catalytic capabilities for specific electrocatalytic reactions by varying the type, area and degree of doping of heteroatoms.

Although these carbon materials are being actively studied as HER catalysts, conventional carbon-based electrocatalysts show limitations in the synthesis process. For example, CVD-graphene-based catalysts are expensive, and there is a problem in that a cumbersome process is required because several gas sources are required to control the pressure and transfer process after synthesis. To solve this problem, oxidized graphene-based catalysts are being studied as alternative candidates, but there are still many challenges and obstacles for the development of efficient carbon-based HER catalysts because of the problems that synthesis takes a lot of time, has toxicity, and has high heat generation. there is a situation.

Republic of Korea Patent No. 10-1860763

The technical problem to be achieved by the present invention is an electrocatalyst for hydrogen generation reaction having high electrochemical properties while being able to be manufactured through a simple process that can replace the conventional expensive noble metal catalyst and solve the problems of the conventional carbon-based catalyst, and To provide a manufacturing method thereof.

The technical problems to be achieved by the present invention are not limited to the technical problems mentioned above, and other technical problems not mentioned can be clearly understood by those of ordinary skill in the art to which the present invention belongs from the description below. There will be.

In order to achieve the above technical object, an embodiment of the present invention provides an electrocatalyst for hydrogen generation reaction comprising a nitrogen-doped polydopamine carbide nano-carbon structure.

The carbonized polydopamine nano-carbon structure may be calcined under a nitrogen atmosphere using polydopamine as a precursor, and nitrogen-doped and carbonized.

The carbonized polydopamine nano-carbon structure may include a partial structure represented by the following Chemical Formula 1.

[Formula 1]

The carbonized polydopamine nano carbon structure may be characterized in that it has a multi-layered film form with an interlayer distance of 0.1 nm to 1 nm.

The film may have a thickness of 5 nm to 40 nm.

The polydopamine carbide nano-carbon structure may be characterized in that it is possible to generate hydrogen gas from water with an overpotential of 151 mV or less at an electrode current density of 10 mA/cm ² or more.

In order to achieve the above technical object, another embodiment of the present invention provides a method for producing an electrocatalyst for hydrogen generation reaction comprising a nitrogen-doped polydopamine carbide nano-carbon structure.

The method for producing an electrocatalyst for hydrogen generation reaction comprising the nitrogen-doped polydopamine carbide nano-carbon structure comprises: polymerizing a polydopamine film to form a polydopamine film by self-polymerizing dopamine on a substrate; Carbonizing the polydopamine film by calcining the polymerized polydopamine film under a nitrogen atmosphere to dope nitrogen and carbonize; a carbonized polydopamine film wafer transfer step of transferring the carbonized polydopamine film to a wafer; and obtaining a carbonized polydopamine nano-carbon film to obtain the transferred carbonized polydopamine film.

The substrate of the polydopamine film polymerization step may be a metal substrate including at least one selected from the group consisting of copper, iron, aluminum, silver, gold, nickel, tin, palladium, and platinum.

In the polydopamine film polymerization step, it may be characterized in that polydopamine is polymerized through the reaction of Scheme 1 below.

[Scheme 1]

The polydopamine film carbonization step may be characterized in that it is carried out by heating to 500 ℃ to 1000 ℃ under a nitrogen atmosphere.

In the carbonizing step of the polydopamine film, it may be characterized in that polydopamine is carbonized through the reaction of Scheme 2 below.

[Scheme 2]

The wafer of the polydopamine carbide film wafer transfer step is sapphire (Al ₂ O ₃ ), silicon, gallium arsenide (GaAs), gallium nitride (GaN) and zinc nitride (ZnN) any one or more selected from the group consisting of It may be characterized by including.

According to an embodiment of the present invention, it is possible to provide an efficient electrocatalyst for hydrogen generation reaction and a method for preparing the same, which can be produced through a simple process and have excellent electrochemical properties.

It should be understood that the effects of the present invention are not limited to the above-described effects, and include all effects that can be inferred from the configuration of the invention described in the detailed description or claims of the present invention.

1 is a flowchart schematically illustrating a method for preparing an electrocatalyst for hydrogen generation reaction including a nitrogen-doped polydopamine carbide nano-carbon structure according to another embodiment of the present invention.
2 is a view showing an optical image and a tapping mode atomic force microscope (AFM) image of the PDA film according to Comparative Example 1 and the C-PDA film according to Example 1 of the present invention.
3 is a view showing a high-resolution transmission electron microscope (TEM) image of the C-PDA film according to Example 1 of the present invention.
4 is a Raman spectrum and X-ray photoelectron spectroscopy measurement graph of a PDA film according to Comparative Example 1 and a C-PDA film according to Example 1 of the present invention.
5 is a graph showing a hydrogen evolution reaction polarization curve in a three-electrode system using each of the catalysts.
6 is a graph showing an overpotential value at 10 mA/cm ² in a three-electrode system using each of the catalysts.
7 is a graph showing a Tapel slope in a three-electrode system using each of the catalysts.
8 shows -0.15 V and -0.20 V vs. -0.20 V measured for 10 hours, respectively. A graph showing the chronoamperometric method of the C-PDA electrocatalyst in RHE.

Hereinafter, the present invention will be described with reference to the accompanying drawings. However, the present invention may be embodied in several different forms, and thus is not limited to the embodiments described herein. And in order to clearly explain the present invention in the drawings, parts irrelevant to the description are omitted, and similar reference numerals are attached to similar parts throughout the specification.

Throughout the specification, when a part is said to be “connected (connected, contacted, coupled)” with another part, it is not only “directly connected” but also “indirectly connected” with another member interposed therebetween. "Including cases where In addition, when a part "includes" a certain component, this means that other components may be further provided, rather than excluding other components, unless otherwise stated.

The terminology used herein is used only to describe specific embodiments, and is not intended to limit the present invention. The singular expression includes the plural expression unless the context clearly dictates otherwise. In the present specification, terms such as “comprise” or “have” are intended to designate that a feature, number, step, operation, component, part, or combination thereof described in the specification exists, but one or more other features It should be understood that this does not preclude the existence or addition of numbers, steps, operations, components, parts, or combinations thereof.

Hereinafter, embodiments of the present invention will be described in detail with reference to the accompanying drawings.

An electrocatalyst for hydrogen generation reaction according to an embodiment of the present invention will be described.

In the present invention, the electrocatalyst for the hydrogen generation reaction is characterized in that it comprises a nitrogen-doped polydopamine carbide nano-carbon structure.

At this time, the carbonized polydopamine nano-carbon structure may be characterized in that it is nitrogen-doped and carbonized by calcination in a nitrogen atmosphere using polydopamine as a precursor.

In addition, the carbonized polydopamine nano-carbon structure may be characterized in that it includes a partial structure represented by the following formula (1).

[Formula 1]

In Formula 1,

n is a natural number greater than or equal to 1.

Polydopamine used as a precursor of the electrocatalyst for the hydrogen generation reaction of the present invention is a self-polymerized polymer of dopamine, and the dopamine is a living body that mimics the adhesive material found in mussels in nature. It is a friendly polymer material. Dopamine has both catechol and amine, which are important chemical functional groups that show adhesion in adhesive proteins, and thus has strong adhesion to organic and inorganic substances. Thus, dopamine not only functions for many applications, but can also serve as a good carbon source for manufacturing carbon-based materials.

Paying attention to this, the inventors of the present invention use polydopamine, which is a biocompatible material with high adhesion, and calcinate it in a nitrogen atmosphere to doping and carbonizing it with nitrogen, thereby inventing an efficient catalyst for hydrogen generation reaction with excellent electrochemical properties came to

As described above, as the conventional carbon-based catalyst for hydrogen generation reaction, graphene material based on chemical vapor deposition (CVD) was mainly used, which is not only expensive, but also for pressure control and transfer process after synthesis. Since it requires several gas sources, a cumbersome process is required, so there are many restrictions to be used as a catalyst for efficient hydrogen generation.

In contrast, dopamine used for the preparation of the catalyst of the present invention can be prepared through a considerably easier process than the conventional carbon-based catalyst because it can form polydopamine by self-polymerizing in aqueous solution conditions. More specifically, the polydopamine may be formed into a polydopamine nano-carbon structure in the form of a film by self-polymerizing dopamine through a dipping process of depositing dopamine on a substrate in an aqueous solution state. In this process, the polydopamine nano carbon structure film is formed on the substrate to have a laminated form in a multi-layered structure.

In this case, the carbonized polydopamine nano carbon structure film may be characterized in that the interlayer distance is multi-layered to 0.1 nm to 1 nm.

If the interlayer distance is less than 0.1 nm, it is not preferable because the catalyst properties are deteriorated.

If the interlayer distance is more than 1 nm, it is not preferable because charge transfer between catalysts is difficult.

Therefore, the carbonized polydopamine nano-carbon structure film is most preferably multi-layered with an interlayer distance of 0.1 nm to 1 nm in view of the effect of the present invention.

In addition, the carbonized polydopamine nano-carbon structure, by controlling the deposition time during the process in which dopamine is deposited on the substrate and controlling the carbonization process conditions, the carbonized polydopamine nano-carbon structure has a thin thickness of the nano-sized thickness. can be freely controlled. Therefore, the ultra-thin carbonized polydopamine nano-carbon structure manufactured to have a thin thickness through the above carbonization process can provide a shorter path for charge transfer from the bulk material to the reaction site located on the surface, so the charge carrier is a material And since it is possible to reach the active site by moving more rapidly from the surface, there is an effect of improving the efficiency of the electrocatalyst.

More specifically, the polydopamine nano carbon structure film may be characterized in that it has a thickness of 5 nm to 40 nm.

If the thickness of the film is less than 5 nm, it is not preferable because the thickness of the film is too thin and mechanical stability such as durability of the catalyst may be deteriorated.

If the film thickness is more than 40 nm, it is not preferable because a short enough distance for improving the above-described catalyst efficiency cannot be provided.

Therefore, the polydopamine nano carbon structure film, it is most preferable in terms of the effect of the present invention to have a thickness of 5nm to 40nm.

Therefore, the polydopamine nano-carbon structure film of the present invention enables the formation of a multi-layer structure through the nano-sized thickness control as described above, so it is possible to broaden the scope of performance improvement in electrical properties compared to the conventional carbon-based catalyst. has

In addition, the polydopamine nano carbon structure is characterized in that it is nitrogen-doped and carbonized by being polymerized using dopamine as described above and then calcined under a nitrogen atmosphere, that is, heat-treated.

The carbonized polydopamine nano-carbon structure of the present invention calcined under a nitrogen atmosphere as described above has a higher nitrogen content compared to a carbon catalyst using conventional graphene doping nitrogen. Therefore, since the active site of the catalyst can be greatly increased, as described above, it is possible to serve as an efficient catalyst capable of generating hydrogen gas even at a low overpotential and having excellent electrical properties.

More specifically, in the polydopamine nano-carbon structure doped with nitrogen and carbonized as described above, the electrocatalyst for hydrogen generation reaction of the present invention has a low overpotential of 151 mV or less at an electrode current density of 10 mA/cm ² or more. to be able to create

Due to the above structural characteristics, according to an embodiment of the present invention, it is possible to provide an efficient electrocatalyst for hydrogen generation reaction having excellent electrochemical properties while being able to be manufactured through a simple process.

A method of manufacturing an electrocatalyst for hydrogen generation reaction including a nitrogen-doped polydopamine carbide nano-carbon structure according to another embodiment of the present invention will be described.

1 is a flowchart schematically illustrating a method for preparing an electrocatalyst for hydrogen generation reaction including a nitrogen-doped polydopamine carbide nano-carbon structure according to another embodiment of the present invention.

Referring to FIG. 1 , in the method for preparing an electrocatalyst for hydrogen generation reaction including a nitrogen-doped polydopamine carbide nano-carbon structure according to another embodiment of the present invention, a polydopamine film is formed by self-polymerizing dopamine on a substrate. Polydopamine film polymerization step (S100); carbonizing the polydopamine film by calcining the polymerized polydopamine film under a nitrogen atmosphere to dope nitrogen and carbonize the polydopamine film (S200); a carbonized polydopamine film wafer transfer step of transferring the carbonized polydopamine film to a wafer (S300); and a carbonized polydopamine nano-carbon film obtaining step (S400) of obtaining the transferred carbonized polydopamine film.

The polydopamine film polymerization step (S100) is a preparation step of an aqueous solution containing dopamine; and dipping the substrate in the aqueous solution.

More specifically, in the polydopamine film polymerization step (S100), it may be characterized in that polydopamine is polymerized through the reaction of Scheme 1 below.

[Scheme 1]

Since dopamine used for polymerization of polydopamine is characterized in that it can be polymerized by itself without mechanical stirring in aqueous solution conditions, an aqueous solution containing dopamine is prepared as described above, and the substrate on which dopamine is to be polymerized is dipping (dipping). ), dopamine self-polymerizes on the substrate at room temperature without additional mechanical stirring. Therefore, due to the above structural characteristics, there is an effect that it is possible to easily prepare a carbon precursor for the preparation of the catalyst of the present invention without the cumbersome process required for the preparation of the conventional carbon-based catalyst.

At this time, if the substrate of the polydopamine film polymerization step is a metal substrate including at least one selected from the group consisting of copper, iron, aluminum, silver, gold, nickel, tin, palladium and platinum, it can be used without limitation. there is.

The polydopamine film carbonization step (S200) may be performed by heating at 500° C. to 1000° C. under a nitrogen atmosphere, and most preferably, heating at 800° C. may be performed.

More specifically, in the step of carbonizing the polydopamine film, polydopamine may be carbonized through the reaction of Scheme 2 below.

[Scheme 2]

As described above, by calcining the polydopamine film self-polymerized in the polydopamine film polymerization step (S200) by heat treatment in a nitrogen atmosphere as described above, the conventional carbon-based catalyst is a complex process that requires several gas sources. Contrary to requiring a catalyst, it can be prepared to have a higher nitrogen content than a conventional catalyst even through a simple process. Therefore, since the active site of the catalyst can be significantly increased, it is possible to produce hydrogen gas at a low overpotential, specifically, an overpotential of 151 mV or less at an electrode current density of 10 mA/cm ² or more, and it is possible to produce a catalyst with efficient and excellent electrical properties. possible.

The carbonized polydopamine film wafer transfer step (S300), spin coating a polymer compound containing PMMA on the substrate on which the polydopamine film is polymerized in the polydopamine film polymerization step; and immersing the substrate on which the polydopamine film on which the polymer compound is spin-coated is polymerized in an acidic solution to remove the substrate; depositing the polydopamine film spin-coated with the polymer compound from which the substrate has been removed on a wafer; removing the polymer compound using an organic solvent; and obtaining a wafer on which the polydopamine film remaining after removing the polymer compound is deposited.

At this time, the wafer of the polydopamine carbide film wafer transfer step is sapphire (Al ₂ O ₃ ), silicon, gallium arsenide (GaAs), gallium nitride (GaN) and zinc nitride (ZnN) any one selected from the group consisting of may include more than one.

Due to the above structural characteristics, according to an embodiment of the present invention, there is an effect that it is possible to provide an efficient electrocatalyst for hydrogen generation reaction that requires a simple process and has excellent electrochemical properties and a method for preparing the same.

Hereinafter, the present invention will be described in more detail through Preparation Examples, Comparative Examples and Experimental Examples. However, the present invention is not limited to the following Preparation Examples and Experimental Examples.

<Production Example 1>

An electrocatalyst for hydrogen generation reaction including nitrogen-doped polydopamine carbide nano-carbon structure according to an embodiment of the present invention was prepared.

The catalyst was prepared in the following way.

First, a copper foil substrate ultrasonically cleaned in acetone, isopropanol, and deionized water (DI water) was dipped in 45 ml of Tris buffer (Tris buffer, tris (hydroxymethyl) aminomethane solution, 10 mM) containing 2 mg of dopamine chloride. (dipping). The pH value of the Tris buffer was adjusted to 8.5 using HCl, and coating polymerization was performed at 25° C. without mechanical polymerization. After 1 hour, the substrate was taken out, washed with purified water, and dried in an oven at 70° C. overnight to obtain a copper substrate (PDA/copper) on which a polydopamine film was deposited.

The PDA/copper was heat-treated at a rate of 10° C./min under flowing nitrogen using a tube furnace. The heat treatment was performed at 800° C. for 1 hour, and then naturally cooled to room temperature to carbonize the polydopamine to obtain a copper substrate (C-PDA/copper) on which a carbonized polydopamine film was deposited.

Then, polymethylmethacrylic acid (PMMA) was spin-coated on the C-PDA/copper. The PMMA/C-PDA/copper substrate on which the PMMA was spin-coated was deposited in a diluted ammonium persulfate solution of 0.2M to remove the copper substrate. The PMMA/C-PDA from which the copper substrate was removed was washed with purified water and then deposited on a Si wafer. Then, by removing the PMMA using acetone, the nitrogen-doped polydopamine carbide nano-carbon structure of the present invention deposited on a Si wafer, that is, a C-PDA film was prepared.

<Comparative Example 1>

In Preparation Example 1, a PDA film was manufactured through the same process as in Preparation Example 1, except that the process of carbonizing the PDA/copper was omitted and immediately transferred to a Si wafer.

<Experimental Example 1>

In order to analyze the shape and structure of the nitrogen-doped polydopamine carbide nano-carbon structure doped with nitrogen of the present invention, optical images of the PDA film and C-PDA film prepared in Comparative Example 1 and Preparation Example 1, tapping mode (Tapping-mode) An atomic force microscope (AFM) image and a high-resolution transmission electron microscope (TEM) image of the C-PDA film were taken and analyzed.

2 is a view showing an optical image and a tapping mode atomic force microscope (AFM) image of the PDA film according to Comparative Example 1 and the C-PDA film according to Example 1 of the present invention.

2 (a) to (c) are views showing an optical image and a tapping mode atomic force microscope (AFM) image of the PDA film according to Comparative Example 1 of the present invention.

2 (d) to (f) are views showing an optical image and a tapping mode atomic force microscope (AFM) image of the PDA film according to Example 1 of the present invention.

2 (g) and (h) are views showing a high-resolution transmission electron microscope (TEM) image of the PDA film according to Example 1 of the present invention.

3 is a view showing a high-resolution transmission electron microscope (TEM) image of the C-PDA film according to Example 1 of the present invention.

2 and 3, the PDA film according to Comparative Example 1 has a thickness of about 31 nm, unlike the formation of a uniform coating on the Si substrate, the C-PDA film according to Preparation Example 1 of the present invention in which it is carbonized It can be seen that decreases to about 12 nm. In addition, it can be seen that the C-PDA film according to Preparation Example 1 of the present invention has a layered structure by looking at the distribution of various dark regions in the TEM image, and the distance between the layers is about 0.34 nm.

Due to this, it can be expected that the layered film of the present invention not only functions as a support layer having high conductivity, but also contains uniform micropores in the film plane of the carbonized C-PDA film. Therefore, the C-PDA of the present invention having such a structure will be advantageous for mass transfer and gas diffusion as an electrocatalyst. In addition, since it has a thin thickness through the above carbonization process, this ultra-thin C-PDA provides a shorter path for charge transfer from the bulk material to the reaction site located on the surface, so that the charge carriers are more It can be confirmed that the efficiency of the electrocatalyst can be improved because it can move rapidly to reach the active site.

<Experimental Example 2>

In order to analyze the structure and electronic properties of the nitrogen-doped polydopamine carbide nano-carbon structure of the present invention, an experiment was performed with Raman spectra and X-ray photoelectron spectroscopy (XPS).

4 is a Raman spectrum and X-ray photoelectron spectroscopy measurement graph of a PDA film according to Comparative Example 1 and a C-PDA film according to Example 1 of the present invention.

Referring to FIG. 4 , it can be confirmed that the PDA has a structure in which C-PDA is calcined under a nitrogen atmosphere and doped with a hetero atom, that is, nitrogen. Such doped nitrogen has a high electronegativity and thus has advantageous properties for hydrogen production. Therefore, it can be confirmed that the C-PDA film of the present invention will have improved electrocatalytic properties.

<Experimental Example 3>

An experiment was conducted to analyze the electrochemical performance of the electrocatalyst for hydrogen generation reaction including the nitrogen-doped polydopamine carbide nano-carbon structure of the present invention. For this, electrochemical measurements were performed using a CHI 780 electrochemical analyzer (CHInstruments, Inc. Austin, TX, USA) using a standard 3-electrode cell. At this time, platinum foil and Ag/AgCl (3M NaCl) were used as a counter electrode and a reference electrode, respectively, and the working electrode was a glassy carbon (GC) tip of a rotating disk electrode (RDE, performed at 1000 rpm at a rate of 5 mV/s). (5.0 mm in diameter) was used.

Each of PDA and C-PDA was deposited on the GC at a catalyst loading of 0.13 mg/cm ² , and analyzed by a three-electrode system using this as a working electrode.

In addition, for comparison, free catalyst-free carbon (bare CG) and Pt/C were mixed with a NAFION solution (5 wt %, Alfa, Seoul, Korea) to form a well-dispersed catalyst ink, and 10 μl of free carbon A work electrode prepared by drop-casting on the tip of (glassy carbon, GC) was similarly analyzed with a three-electrode system.

5 is a graph showing a hydrogen evolution reaction polarization curve in a three-electrode system using each of the catalysts.

Referring to FIG. 5 , in the case of an initial overpotential (ie, overpotential at 1.0mA/cm ² ), the PDA shows a high value of 176mV, which is similar to the overpotential value of 203mV of the bare CG. On the other hand, since the onset overpotential of C-PDA has a very low value of 68 mV, it can be confirmed that C-PDA has very suitable catalytic properties for use in an acidic medium. In addition, it can be seen that the operating potential of the C-PDA is also -0.13V, which is much lower than the -0.28V of the PDA.

6 is a graph showing an overpotential value at 10 mA/cm ² in a three-electrode system using each of the catalysts.

Referring to FIG. 6 , the overpotentials of the PDA and C-PDA at 10 mA/cm ² are 306 mV and 151 mV, respectively, confirming that the C-PDA has a very low overpotential value compared to the PDA.

7 is a graph showing a Tapel slope in a three-electrode system using each of the catalysts.

Referring to FIG. 7 , it can be seen that C-PDA has a low Tafel slope value of 45 mV/decade, which is smaller than PDA (74 mV/decade) and somewhat similar to the value of Pt/C (42 mV/decade). Therefore, it can be confirmed that the C-PDA catalyst of the present invention has a low Tafel slope value comparable to that of the noble metal platinum catalyst.

8 shows -0.15V and -0.20V vs. each measured for 10 hours. A graph showing the chronoamperometric method of C-PDA electrocatalyst in RHE.

Referring to FIG. 8 , it can be seen that the C-PDA electrocatalyst of the present invention maintains an initial current density value of about -20 mA/cm ² or more of 80% for 10 hours, which is the C-PDA electrocatalyst of the present invention It can be seen that has very stable long-term durability.

The above description of the present invention is for illustration, and those of ordinary skill in the art to which the present invention pertains can understand that it can be easily modified into other specific forms without changing the technical spirit or essential features of the present invention. will be. 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 dispersed form, and likewise components described as distributed may be implemented in a combined form.

The scope of the present invention is indicated by the following claims, and all changes or modifications derived from the meaning and scope of the claims and their equivalents should be construed as being included in the scope of the present invention.

Claims (12)

An electrocatalyst for hydrogen generation reaction comprising a nitrogen-doped polydopamine carbide nano-carbon structure.
According to claim 1,
The carbonized polydopamine nano carbon structure is an electrocatalyst for hydrogen generation reaction, characterized in that it is calcined in a nitrogen atmosphere using polydopamine as a precursor, and is nitrogen-doped and carbonized.
According to claim 1,
The carbide polydopamine nano-carbon structure, an electrocatalyst for hydrogen generation reaction, characterized in that it comprises a partial structure represented by the following formula (1).
[Formula 1]

In Formula 1,
n is a natural number greater than or equal to 1.
According to claim 1,
The carbonized polydopamine nano carbon structure is an electrocatalyst for hydrogen generation reaction, characterized in that it has a multi-layered film form with an interlayer distance of 0.1 nm to 1 nm.
5. The method of claim 4,
The film is an electrocatalyst for hydrogen generation reaction, characterized in that it has a thickness of 5 nm to 40 nm.
According to claim 1,
The carbonized polydopamine nano-carbon structure is an electrocatalyst for hydrogen generation reaction that enables generation of hydrogen gas from water with an overpotential of 151 mV or less at an electrode current density of 10 mA/cm ² or more.
Polydopamine film polymerization step of forming a polydopamine film by self-polymerizing dopamine on a substrate;
carbonizing the polydopamine film by calcining the polymerized polydopamine film under a nitrogen atmosphere to dope nitrogen and carbonize;
a carbonized polydopamine film wafer transfer step of transferring the carbonized polydopamine film to a wafer; and
A method for producing an electrocatalyst for hydrogen generation reaction comprising a nitrogen-doped polydopamine carbide nano-carbon structure comprising a;
8. The method of claim 7,
The substrate of the polydopamine film polymerization step is nitrogen doped, characterized in that it is a metal substrate comprising at least one selected from the group consisting of copper, iron, aluminum, silver, gold, nickel, tin, palladium and platinum. A method for producing an electrocatalyst for hydrogen generation reaction comprising a carbonized polydopamine nano-carbon structure.
8. The method of claim 7,
In the polydopamine film polymerization step, polydopamine is polymerized through the reaction of Scheme 1 below.
[Scheme 1]

8. The method of claim 7,
The polydopamine film carbonization step is a method of producing an electrocatalyst for hydrogen generation reaction comprising a nitrogen-doped polydopamine nano-carbon structure, characterized in that it is carried out by heating to 500 ℃ to 1000 ℃ under a nitrogen atmosphere.
8. The method of claim 7,
In the carbonization of the polydopamine film, the method for producing an electrocatalyst for hydrogen generation reaction comprising a nitrogen-doped carbonized polydopamine nano-carbon structure, characterized in that polydopamine is carbonized through the reaction of Scheme 2 below.
[Scheme 2]

8. The method of claim 7,
The wafer of the polydopamine carbide film wafer transfer step includes at least one selected from the group consisting of sapphire (Al2O3), silicon, gallium arsenide (GaAs), gallium nitride (GaN), and zinc nitride (ZnN). Method for producing an electrocatalyst for hydrogen generation reaction comprising a nitrogen-doped polydopamine carbide nano-carbon structure, characterized in that.

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