Hybrid electrode containing plasmon nanoparticles and electrolysis system containing same

Abstract

The invention relates to a mixed electrode containing plasmon nanoparticles and an electrolysis system containing the electrode. According to the mixed electrode and the electrolysis system comprising the electrode, the surface of a catalyst can be reactivated in an electrochemical reaction by means of a plasmon phenomenon by utilizing a plasmon-reactor combined electrode.

Description

Technical Field

[0001] This application relates to a hybrid electrode containing plasmonic nanoparticles and an electrolysis system containing the electrode. Background Technology

[0002] To improve the energy density per unit volume during hydrogen transportation, it is typically transported as a liquid hydrogen carrier. This is because the storable amount of gaseous hydrogen is limited, making it difficult to transport large quantities. Therefore, liquefied hydrogen, ammonia, and liquid organic hydrogen carriers (LOHCs) have attracted considerable attention as methods for hydrogen storage and transportation. Among these, the use of ammonia for hydrogen storage, transportation, and extraction is particularly noteworthy, as it can store approximately 1.7 times more hydrogen than liquefied hydrogen. Furthermore, the global import and export of ammonia is active, and its production facilities and transport vessels are well-developed, ensuring the economic viability of hydrogen supply when using ammonia as a hydrogen carrier.

[0003] Methods for producing hydrogen from ammonia can be broadly categorized into thermal decomposition, alkali metal imide methods, and water electrolysis. Thermal decomposition utilizes temperatures above 400°C to decompose ammonia, requiring a catalyst. Alkali metal amide methods utilize the exothermic reaction with alkali metal hydrides to decompose ammonia at room temperature, but suffer from poor economic efficiency. Water electrolysis uses ammonia as an electrolyte; due to its low-temperature operation, it offers good stability and high efficiency. However, most existing inventions related to ammonia-water electrolysis simply utilize the activity of metal catalysts, such as the development of gold-platinum mixed catalysts, photocatalytic hydrogen production, and their application as catalysts in electrochemical ammonia electrolysis.

[0004] Prior technology documents

[0005] Patent documents

[0006] Korean Patent Publication No. 2160870. Summary of the Invention

[0007] The problem the invention aims to solve

[0008] The purpose of this application is to provide a hybrid electrode containing plasmonic nanoparticles and an electrolysis system containing the electrode.

[0009] However, the problems to be solved by this application are not limited to those mentioned above, and other problems not mentioned can be clearly understood by those skilled in the art from the following description.

[0010] Solution for solving the problem

[0011] A first aspect of this application provides a hybrid electrode comprising: a substrate; a catalyst layer formed on the substrate; and plasmonic nanoparticles formed on the catalyst layer; wherein electrons generated by plasmon resonance of the plasmonic nanoparticles are transferred to the catalyst layer.

[0012] A second aspect of this application provides an electrolysis system comprising: a hybrid electrode including a substrate, a catalyst layer formed on the substrate, and plasmonic nanoparticles formed on the catalyst layer; a cathode electrode; and an electrolyte containing a substance to be electrolyzed, wherein the hybrid electrode, acting as an anode electrode, undergoes an oxidation reaction of the substance to be electrolyzed, and electrons generated by the plasmonic phenomenon of the plasmonic nanoparticles are transferred to the catalyst layer, causing an oxidation reaction intermediate to desorb from the catalyst layer.

[0013] A third aspect of this application provides an electrolysis method comprising: supplying power to an electrolysis system according to the second aspect and subjecting it to light irradiation; and obtaining hydrogen (H2) at the cathode electrode.

[0014] A fourth aspect of this application provides a fuel cell comprising: a hybrid electrode including a substrate, a catalyst layer formed on the substrate, and plasmonic nanoparticles formed on the catalyst layer; a cathode electrode; and an electrolyte layer, wherein the hybrid electrode, as an anode electrode, undergoes an oxidation reaction of fuel, and electrons generated by the plasmonic phenomenon of the plasmonic nanoparticles are transferred to the catalyst layer, causing oxidation reaction intermediates to desorb from the catalyst layer.

[0015] Invention Effects

[0016] According to the hybrid electrode and electrolysis system including the electrode according to the embodiments of this application, the surface of the catalyst can be reactivated in the electrochemical reaction by means of the plasmon phenomenon using the plasmon composite electrode.

[0017] According to the electrolysis system of this application, electrons generated by plasmon excitation of plasmon nanoparticles are transferred to the catalyst layer, causing oxidation reaction intermediates to desorb from the catalyst layer, thereby improving the activity and lifespan of the electrode. Attached Figure Description

[0018] Figure 1Figures a through f illustrate a schematic diagram of the synthesis process of an electrodeposited Pt (reactor)-Au (antenna) catalyst in one embodiment of this application: (a) X-ray diffraction (XRD) patterns of each electrode comprising Ti fiber felt, Pt on Ti felt, and Pt-Au on Ti felt; (b) Scanning electron microscope (SEM) images of Pt on Ti felt (c and d); and SEM images of Pt-Au on Ti felt (e and f) (the inset in f shows the atomic proportions of each element in the scanning electron microscope-energy dispersive spectroscopy (SEM-EDS) profile).

[0019] Figures 2a to 2h A schematic diagram (2a) of the electrolysis system in one embodiment of this application is shown; X-ray near-edge absorption structures (XANES) and Pt L3 under ex-situ (2b and 2c), in-situ (2d and 2e), and operando (2g and 2h) conditions are also shown. - The corresponding k³-weighted Fourier transform (FT) of the edge-extended XAFS (EXAFS) spectrum (inset shows the magnified front XANES region); and the wavelet transform (WT) of the k³-weighted EXAFS spectra at -0.2V and -0.2V under plasmon excitation conditions (2f).

[0020] Figures 3a to 3i The following figures are shown in one embodiment of this application: Cyclic voltammetry (CV) curves measured at room temperature using an H-type battery in 1M KOH and 0.5M NH4OH on a Pt-Au electrode, with or without light irradiation (3a); Chronopotentiometry at a constant current density of 1 mA cm⁻² with or without light irradiation (3b); CV curve after short-term stability measurement (3c); Electrochemical double layer capacitance (C0). dl (3d); Peak current density of each electrode with peak potential under dark or light irradiation conditions (3e); Normalized peak current density of electrochemical active surface area (ECSA) of Pt and Pt-Au electrodes (3f); Specific activity at various applied potentials (3g and 3h); and plasmon enhancement of ammonia oxidation activity (3i).

[0021] Figures 4a to 4cThe following are shown in one embodiment of this application: using an H-type battery, the surface temperature of the electrode obtained according to the light irradiation intensity (4a); the stability results of the ammonia electrolysis current density obtained by adjusting only the presence or absence of light irradiation and the electrolyte temperature (4b); and the stability results of the ammonia electrolysis current density obtained according to the light irradiation intensity (4c) (the ammonia electrolysis driving conditions were carried out at -0.2V vs. Ag / AgCl as the ammonia electrolysis driving conditions).

[0022] Figures 5a to 5d This application illustrates, in one embodiment, the electrochemical double-layer capacitance (C) of the electrode surface under H-type cells in the absence of light irradiation (5a), under conditions of electrolyte temperature rise (5b), and under light irradiation (5c). dl The results of the analysis; and the results of the calculation of the electrochemical double-layer capacity (5d) (indicating the highest electrochemical surface area under light irradiation).

[0023] Figures 6a to 6f This application illustrates, in one embodiment, the process of a continuous ammonia oxidation reaction (AOR) performed on a reference electrode Ag / AgCl under dark chamber, temperature control, and plasmon excitation conditions (6a); the amount of NH3 reacting during the continuous AOR process under dark chamber and light irradiation (6b); the amount of NH3 reacting during the continuous AOR process under redox AOR and light irradiation (6c); the cycling curve (6d); the durability curve including the oxidation kinetics for AOR and the total amount of NH3 reacted (6e); and the charge consumed during oxidation and reduction (6a). QOx. and Q Red.) The difference and ratio between them (6f). Detailed Implementation

[0024] The embodiments of this application are described in detail below with reference to the accompanying drawings, so that those skilled in the art can easily implement them. This application can be implemented in many different forms and is not limited to the embodiments described herein; and in the accompanying drawings, parts unrelated to the description are omitted for clarity, and similar reference numerals are used to label similar parts throughout the specification.

[0025] Throughout this application, when referring to the “connection” of one part to another, it includes not only the case of “direct connection”, but also the case of “electrical connection” with other components in between.

[0026] Throughout this application, when it is mentioned that a component is "on" another component, it includes not only the case where the component is in direct contact with the other component, but also the case where there are other components between the two components.

[0027] Throughout this application, when a part is referred to as "containing" a certain element, unless otherwise stated, it means that other elements may also be included, rather than that other elements are excluded.

[0028] The degree terms “about” and “substantially” used in this specification are used to refer to the inherent manufacturing and material tolerances, meaning them in terms of their numerical values ​​or close to those values. They are also used to prevent unscrupulous infringers from improperly using the disclosed content which contains accurate or absolute values, and to help understand this application.

[0029] The degree terms “~ step” or “~ step” used throughout this application do not mean “the step used for ~”.

[0030] Throughout this application, the term "combination of them" in the Markush form of the expression refers to a mixture or combination of one or more of the constituent elements described in the Markush form of the expression, meaning that it includes one or more of the constituent elements selected from the group.

[0031] Throughout this application, the reference to "A and / or B" means "A or B, or A and B".

[0032] The embodiments of this application are described in detail below, but this application is not limited thereto.

[0033] A first aspect of this application provides a hybrid electrode comprising: a substrate; a catalyst layer formed on the substrate; and plasmonic nanoparticles formed on the catalyst layer, wherein electrons generated by plasmon resonance of the plasmonic nanoparticles are transferred to the catalyst layer.

[0034] In one embodiment of this application, the substrate can be used without limitation as long as it is a substrate that can be used as an electrode in the art. As a non-limiting example, carbon-based materials, metals containing Ti, nickel (Ni) or copper (Cu), inorganic oxides containing oxides such as Ti, Zr, Al or Si, perovskite oxides, or zeolites can be selected.

[0035] In one embodiment of this application, the carbon-based material may include one or more of the following: graphite, carbon fiber, carbon sheet, carbon black, carbon nanotube (CNT), carbon sphere, carbon ribbon, fullerene, active carbon, carbon nanowire, and graphene, but is not limited thereto.

[0036] In one embodiment of this application, the substrate may be in the form of including a space for fluid flow, but is not limited thereto.

[0037] In one embodiment of this application, the substrate may be in the form of a mesh structure, but is not limited thereto.

[0038] In one embodiment of this application, the substrate may be a mesh structure formed by Ti fibers, Ni fibers or Pt fibers, but is not limited thereto.

[0039] In one embodiment of this application, the catalyst layer may contain one or more of platinum (Pt), palladium (Pd), iridium (Ir), silver (Ag), ruthenium (Ru), nickel (Ni), copper (Cu), manganese (Mn), cobalt (Co), iron (Fe), and alloys thereof, but is not limited thereto.

[0040] In one embodiment of this application, the plasmonic nanoparticles may contain one or more of the following: gold (Au), silver (Ag), platinum (Pt), palladium (Pd), rhodium (Rh), rhenium (Re), copper (Cu), aluminum (Al), magnesium (Mg), indium (In), gallium (Ga), nickel (Ni), and rubidium (Rb), but are not limited thereto.

[0041] In one embodiment of this application, the particle size distribution of the plasmonic nanoparticles is about 5 nm to about 140 nm, wherein the number of plasmonic nanoparticles with a particle size of about 40 nm to about 90 nm can be more than 50% of all the plasmonic nanoparticles.

[0042] In one embodiment of this application, the particle size of the plasmonic nanoparticles may vary depending on the light irradiation conditions (light band or type, etc.) when driving the hybrid electrode and / or the type of plasmonic nanoparticles. In one embodiment of this application, as a structural design that can improve surface plasmon efficiency under actual solar irradiation conditions (1 Sun), the average particle size of the plasmonic nanoparticles is about 60 nm to about 80 nm.

[0043] A second aspect of this application provides an electrolysis system comprising: a hybrid electrode including a substrate, a catalyst layer formed on the substrate, and plasmonic nanoparticles formed on the catalyst layer; a cathode electrode; and an electrolyte containing a substance to be electrolyzed, wherein the hybrid electrode, acting as an anode electrode, undergoes an oxidation reaction of the substance to be electrolyzed, and electrons generated by the plasmon resonance of the plasmonic nanoparticles are transferred to the catalyst layer, causing an oxidation reaction intermediate to desorb from the catalyst layer.

[0044] For the parts that overlap with the first aspect of this application, detailed descriptions have been omitted. The same applies to the descriptions of the first aspect of this application, even if the descriptions in the second aspect of this application are omitted.

[0045] In one embodiment of this application, the substance to be electrolyzed may contain NH3 or H2O.

[0046] In one embodiment of this application, when the substance being electrolyzed is NH3, the electrolyte may contain ammonia.

[0047] In one embodiment of this application, when the substance being electrolyzed is NH3, the concentration can be from about 0.1M to about 10M, but is not limited thereto. In another embodiment of this application, when the substance being electrolyzed is NH3, the concentration can be from about 0.1M to about 10M, from about 0.1M to about 5M, from about 0.1M to about 3M, from about 0.1M to about 2M, from about 0.3M to about 10M, from about 0.3M to about 5M, from about 0.3M to about 3M, from about 0.3M to about 2M, from about 0.5M to about 10M, from about 0.5M to about 5M, from about 0.5M to about 3M, or from about 0.5M to about 2M, but is not limited thereto.

[0048] In one embodiment of this application, the electrolyte may further comprise an electrolyte comprising an alkali metal hydroxide.

[0049] In one embodiment of this application, the alkali metal hydroxide may contain one or more selected from KOH, NaOH and Ca(OH)2, but is not limited thereto.

[0050] In one embodiment of this application, the concentration of the alkali metal hydroxide can be from about 0.1 M to about 10 M, but is not limited thereto.

[0051] In one embodiment of this application, in the electrolysis system, when the substance being electrolyzed is NH3, an ammonia oxidation reaction can occur at the anode electrode to generate nitrogen and water, and a water reduction reaction can occur at the cathode electrode to generate hydrogen. In this case, the reaction equations at the anode and cathode electrodes are as follows:

[0052] Anode electrode: 2NH3 + 6OH- - → N2 + 6H2O + 6e -

[0053] Cathode electrode: 6H₂O + 6e⁻ - → 3H2 + 6OH -

[0054] In one embodiment of this application, in the electrolysis system, when the substance being electrolyzed is NH3, nitrogen oxides (NO3) are continuously generated on the catalyst layer due to the strong N-bonding interaction generated at the anode electrode. x The nitrogen oxides can clog the active surface of the catalyst, leading to a decrease in the catalyst activity of the electrode. In the electrolysis system according to embodiments of this application, electrons generated by the plasmon resonance of the plasmon nanoparticles are transferred to the catalyst layer, causing the nitrogen oxide intermediates to desorb from the catalyst layer, thereby improving the activity and lifespan of the electrode.

[0055] In one embodiment of this application, the electrolysis system may further include a reference electrode. In one embodiment of this application, the reference electrode may include, but is not limited to, an Ag / AgCl (silver / silver chloride) electrode.

[0056] In one embodiment of this application, the electrolysis system may further include a diaphragm.

[0057] In one embodiment of this application, the electrolysis system further includes a diaphragm, thereby forming a structure comprising: an anode electrode portion including the mixed electrode; a cathode electrode portion including the cathode electrode; a diaphragm; a first electrolyte contained in the anode electrode portion; and a second electrolyte contained in the cathode electrode portion, capable of separating and producing hydrogen and nitrogen.

[0058] In one embodiment of this application, the electrolysis system may further include a light irradiation unit.

[0059] In one embodiment of this application, light with a wavelength range of about 200 nm to about 2500 nm can be irradiated by the light irradiation section.

[0060] In one embodiment of this application, the electrolysis system may further include a power supply unit.

[0061] A third aspect of this application provides an electrolysis method comprising: supplying power to an electrolysis system according to the second aspect and subjecting it to light irradiation; and obtaining H2 at the cathode electrode.

[0062] For portions that overlap with the first and second aspects of this application, detailed descriptions have been omitted. However, the content described in the first and second aspects of this application is equally applicable even if its description is omitted in the third aspect of this application.

[0063] In one embodiment of this application, by irradiating the plasmonic nanoparticles with light, the plasmonic phenomenon (localized surface plasmon resonance, LSPR) will be manifested. The excited electrons generated at this time desorb the oxidation reaction intermediates, thereby preventing poisoning.

[0064] In one embodiment of this application, the light irradiation can irradiate light with a wavelength range of about 200 nm to about 2500 nm.

[0065] A fourth aspect of this application provides a fuel cell comprising: a hybrid electrode including a substrate, a catalyst layer formed on the substrate, and plasmonic nanoparticles formed on the catalyst layer; a cathode electrode; and an electrolyte layer, wherein the hybrid electrode, as an anode electrode, undergoes an oxidation reaction of fuel, and electrons generated by the plasmonic phenomenon of the plasmonic nanoparticles are transferred to the catalyst layer, causing oxidation reaction intermediates to desorb from the catalyst layer.

[0066] For the parts that overlap with the first aspect of this application, detailed descriptions have been omitted. However, the content described in the first aspect of this application is equally applicable even if its description is omitted in the fourth aspect of this application.

[0067] The fuel cell of this application may include, without limitation, any fuel cell currently in use that can apply the technical features of this invention.

[0068] In one embodiment of this application, the fuel cell may be a hydrogen fuel cell.

[0069] In one embodiment of this application, the fuel cell can be a polymer electrolyte fuel cell (PEMFC). Typically, when the fuel in a fuel cell contains carbon (C) such as natural gas, the oxidation reaction of natural gas produces CO (carbon monoxide), which is an intermediate in the oxidation reaction. This CO may adsorb onto the catalyst layer of the anode electrode, leading to poisoning and reduced fuel cell performance. According to the fuel cell of this embodiment, electrons generated by the plasmon resonance of the plasmon nanoparticles are transferred to the catalyst layer, causing CO to desorb from the catalyst layer, thereby preventing poisoning.

[0070] The present application will now be described in more detail with reference to the embodiments. However, the embodiments described below are merely examples to help understand the present application, and the content of the present application is not limited to the embodiments described below.

[0071] Forms for implementing the invention

[0072] <Example 1: Preparation of a hybrid electrode comprising a plasmonic antenna (Au) and an ammonia oxidation reactor (Pt)>

[0073] A mesh-structured substrate was fabricated using Ti fibers. Then, Pt was deposited on the Ti fibers via electrodeposition, followed by loading Au nanostructures to prepare a hybrid electrode comprising a plasmonic antenna (Au) and an ammonia oxidation reactor (Pt). Figure 1 (a).

[0074] The detailed process of Pt electrodeposition is as follows:

[0075] 1) It constitutes a batch-type three-electrode electrochemical system.

[0076] -Ti electrode (working electrode)

[0077] -Ag / AgCl electrode (reference electrode)

[0078] - Graphite electrode (counter electrode)

[0079] 2) Immerse the electrode in 5mM H2PtCl6 electrolyte.

[0080] 3) Pt was deposited by cyclic voltammetry at a rate of 100 mV / s within the range of -1.0 V to -0.2 V (vs. Ag / AgCl electrode).

[0081] The detailed process of depositing Au on Pt is as follows:

[0082] 1) It constitutes a batch-type three-electrode electrochemical system.

[0083] - A Pt-on-Ti electrode (working electrode) deposited on Ti.

[0084] -Ag / AgCl electrode (reference electrode)

[0085] - Graphite electrode (counter electrode)

[0086] 2) Immerse the electrode in 1mM HAuCl4 + 0.05M PBS electrolyte.

[0087] 3) Au was deposited by cyclic voltammetry at a rate of 50 mV / s for 80 cycles in the range of -0.855 V to -0.055 V (vs. Ag / AgCl electrode).

[0088] refer to Figure 1 b. This confirms that Pt and Au are deposited on the Ti substrate. (Reference) Figure 1 c to Figure 1 To explain, the average particle size of Au nanoparticles is approximately 70 nm, and the particle size distribution ranges from a minimum of 5 nm to a maximum of 140 nm.

[0089] <Example 2: Manufacturing an ammonia electrolysis system including a hybrid electrode>

[0090] An ammonia electrolysis system was manufactured, comprising: a mixed electrode prepared in Example 1 as the working electrode, a graphite electrode as the counter electrode, an Ag / AgCl electrode as the reference electrode, and an electrolyte containing ammonia water. Figure 2a The electrolysis system is made of polytetrafluoroethylene (PTFE), a material that does not chemically react with the electrolyte. The electrolyte also contains KOH (1M) electrolyte and 0.5M NH4OH. Furthermore, the hybrid electrode was irradiated with light (1 SUN) to stimulate plasmon activity.

[0091] [Experimental Example]

[0092] 1. Electrochemical analysis of ammonia electrolysis reaction (plasmon phenomenon)

[0093] In the ammonia electrolysis system of Example 2, the electrochemical analysis of the ammonia electrolysis reaction was performed depending on whether light irradiation was applied. (Reference) Figures 3a to 3i The study confirmed that the ammonia electrolysis reaction was enhanced before and after the plasmon resonance phenomenon. For Figure 3b Stability tests confirmed that it operates at a constant current (1 mA cm⁻¹). -2 Under these conditions, stability and efficiency were improved within the shaded region. For Figure 3c Cyclic voltammogram tests confirmed that the improved performance of ammonia electrolysis based on plasmon resonance was maintained even after electrode stability testing. Figure 3a and 3c Cyclic voltammetry was performed in a scan range of -0.9V to 0.8V (vs. Ag / AgCl) and at a 20mV / s s⁻¹. -1 Electrochemical reactions were measured at a specific scan rate. Additionally, reference... Figures 3d to 3fThe study confirmed that for a simple Ti support or a Pt electrode with Pt electrodeplasm, the increase in electrochemical double-layer capacitance and ammonia electrolysis under light irradiation is negligible. Plasmon resonance only occurs when Au nanoparticles are loaded onto the surface of the Pt electrode.

[0094] 2. Confirmation of plasmon phenomena

[0095] Confirmation of plasmon resonance phenomenon (temperature change)

[0096] The variation of electrode surface temperature with light intensity during plasmon resonance was confirmed. Figure 4a A comparison of stability test results when simply increasing the electrolyte temperature versus when plasmon resonance was induced revealed that the stability change of the ammonia electrolysis system when simply increasing the electrolyte temperature was minimal. Figure 4b It was confirmed that the ammonia electrolysis process based on plasmon resonance improved the reaction stability of the electrode. Figure 4c This confirms that the increase in electrode surface temperature caused by light irradiation is not the factor that improves the activity and stability of ammonia electrolysis, but rather the electrons generated by the plasmon resonance phenomenon induced by light irradiation are the reason for the improved activity and stability of ammonia electrolysis.

[0097] Confirm plasmon phenomenon (confirm surface area).

[0098] It was confirmed that when plasmon resonance occurred, the electrode's surface area and active sites were increased. Figures 5a to 5d For electrodes where the electrolyte temperature is simply increased, the electrochemical surface area remains unchanged. This confirms that the increased activity and stability of ammonia electrolysis when plasmon resonance occurs stems from the enhanced electrode-electrolyte interaction resulting from the increase in electrochemical double-layer capacitance.

[0099] 3. Surface analysis of ammonia electrolysis reaction (confirmation of surface reactivation)

[0100] Using real-time surface analysis, both real-time and static analyses confirmed that when plasmon resonance occurs in the actual ammonia electrolysis reaction, the number of Pt-N bonds on the surface of the mixed electrode decreases. Figures 2b to 2h This confirms that plasmon resonance directly plays a role in restoring the active sites of the Pt electrode. Figure 2b , Figure 2d and Figure 2g We have grasped the changes in the oxidation state of Pt metal before and after plasmon resonance, through... Figure 2c , Figure 2e and Figure 2h The bonding of Pt metal surfaces before and after plasmon resonance was confirmed. Specifically, through... Figure 2d and Figure 2eThe results confirmed that the Pt-N bonds generated during ammonia electrolysis decreased after plasmon resonance (light irradiation), thus further confirming that the improvement in ammonia electrolysis activity and stability by plasmon resonance stems from the inhibition of surface Pt-N (poisoning). Figure 2f The results provided an intuitive understanding of the degree of change in the Pt surface before and after the plasmon resonance phenomenon.

[0101] 4. Optimization of ammonia electrolysis process based on plasmon resonance (platinon resonance + electrochemistry)

[0102] It was confirmed that when implementing a plasmon-based redox scheme, the amount of ammonia electrolyzed in the same time period was 12 times greater than that driven by simple ammonia electrolysis. Figures 6a to 6f ).for Figure 6a Specifically, the results confirmed that the stability of ammonia electrolysis increases under both plasmon and constant current conditions. Furthermore, when applying schemes based on plasmon phenomena with oxidation (-0.2V vs. Ag / AgCl, 60 seconds) and reduction (-0.8V vs. Ag / AgCl, 6 seconds) conditions, it was confirmed that the stability of ammonia electrolysis under these conditions was improved by approximately 12 times compared to that under constant current conditions. Figure 6c Therefore, it is confirmed that the redox activity remains stable during the execution of the redox protocol, up to approximately 500 cycles. Figure 6d The results confirmed the plasmon-based ammonia electrolysis scheme in which the ammonia electrolysis process proceeded at approximately 4.3 mmol NH3 h⁻¹. -1 cm 2 The electrolysis rate remained stable for approximately 40 hours.

[0103] The foregoing description of this application is exemplary, and those skilled in the art will understand that it can be easily modified into other specific forms without changing the technical concept or essential features of this application. Therefore, the embodiments described above should be understood in all respects as exemplary and not restrictive. For example, the constituent elements described as a single type can be implemented separately, and similarly, the constituent elements described as separate can also be implemented in combination.

[0104] The scope of this application is defined by the scope of the patent claims described below rather than by the detailed description above, and all variations or modifications derived from the meaning and scope of the patent claims and their equivalents shall be interpreted as being included within the scope of this application.

Claims

1. A hybrid electrode comprising: Substrate; A catalyst layer is formed on the substrate; and Plasmon nanoparticles are formed on the catalyst layer. in, Electrons generated by the plasmon resonance phenomenon of the plasmon nanoparticles are transferred to the catalyst layer.

2. The hybrid electrode according to claim 1, wherein, The substrate is in the form of a hollow space for fluid flow.

3. The hybrid electrode according to claim 1, wherein, The catalyst layer comprises one or more of platinum (Pt), palladium (Pd), iridium (Ir), silver (Ag), ruthenium (Ru), nickel (Ni), copper (Cu), manganese (Mn), cobalt (Co), iron (Fe), and their alloys.

4. The hybrid electrode according to claim 1, wherein, The plasmonic nanoparticles comprise one or more of the following: gold (Au), silver (Ag), platinum (Pt), palladium (Pd), rhodium (Rh), rhenium (Re), copper (Cu), aluminum (Al), magnesium (Mg), indium (In), gallium (Ga), nickel (Ni), and rubidium (Rb).

5. The hybrid electrode according to claim 1, wherein, The particle size distribution of the plasmonic nanoparticles ranges from 5 nm to 140 nm, with the number of plasmonic nanoparticles with a particle size of 40 nm to 90 nm accounting for more than 50% of all plasmonic nanoparticles.

6. The hybrid electrode according to claim 1, wherein, The average particle size of the plasmonic nanoparticles is 60 nm to 80 nm.

7. An electrolysis system, comprising: A hybrid electrode comprising a substrate; A catalyst layer is formed on the substrate; And plasmonic nanoparticles are formed on the catalyst layer; Cathode electrode; as well as Electrolyte, containing the substance being electrolyzed. In this process, the hybrid electrode serves as the anode electrode, where the electrolyzed substance undergoes an oxidation reaction. Electrons generated by the plasmon resonance phenomenon of the plasmon nanoparticles are transferred to the catalyst layer, causing the oxidation reaction intermediate to desorb from the catalyst layer.

8. The electrolysis system according to claim 7, wherein, The substance being electrolyzed contains NH3 or H2O.

9. The electrolysis system according to claim 7, wherein, When the substance being electrolyzed is NH3, the concentration is from 0.1M to 10M.

10. The electrolysis system according to claim 7, wherein, The electrolyte also contains an electrolyte containing alkali metal hydroxides.

11. The electrolysis system according to claim 7, wherein, The electrolysis system also includes a light irradiation unit.

12. The electrolysis system according to claim 7, wherein, The electrolysis system also includes a power supply unit.

13. A fuel cell, comprising: A hybrid electrode comprising a substrate, a catalyst layer formed on the substrate, and plasmonic nanoparticles formed on the catalyst layer; Cathode electrode; as well as Electrolyte layer, The hybrid electrode serves as the anode electrode for the oxidation reaction of the fuel. Electrons generated by the plasmon resonance phenomenon of the plasmon nanoparticles are transferred to the catalyst layer, causing the oxidation reaction intermediate to desorb from the catalyst layer.

14. The fuel cell according to claim 13, wherein, The fuel cell is a hydrogen fuel cell.

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