Hybrid electrode comprising plasmonic nanoparticles and electrolytic system comprising same

Abstract

The present application relates to a hybrid electrode comprising plasmonic nanoparticles and an electrolytic system comprising same. The hybrid electrode and the electrolytic system comprising same according to embodiments of the present application may reactivate a catalyst surface by utilizing a plasmonic phenomenon during an electrochemical reaction using a plasmonic-active electrode (antenna-reactor) composite electrode.

Description

Hybrid electrode comprising plasmonic nanoparticles and electrolytic system comprising the same

[0001] The present invention relates to a hybrid electrode including plasmonic nanoparticles and an electrolytic system including the same.

[0002] To increase its volumetric energy density, hydrogen is typically transported as a liquid hydrogen carrier. Gaseous hydrogen has a limited storage capacity, making it difficult to transport large quantities. Consequently, methods utilizing liquefied hydrogen, ammonia, and liquid organic hydrogen carriers (LOHC) for hydrogen storage and transportation are gaining attention. Among these, ammonia-based hydrogen storage, transportation, and extraction are attracting particular attention. Ammonia storage allows for approximately 1.7 times more hydrogen to be stored than liquid hydrogen. Furthermore, the global export and import of ammonia is active, and the infrastructure, including production facilities and transport vessels, is in place. Therefore, utilizing ammonia as a hydrogen carrier can ensure economical hydrogen supply.

[0003] Methods for producing hydrogen from ammonia can be broadly categorized into thermal decomposition, alkali metal amide process, and electrolysis. Thermal decomposition utilizes high temperatures exceeding 400°C to decompose ammonia, necessitating the use of a catalyst. Alkali metal amide process utilizes an exothermic reaction with alkali metal hydride to decompose ammonia at room temperature, but has the disadvantage of low economic efficiency. Electrolysis utilizes ammonia as an electrolyte, and operates at low temperatures, resulting in good stability and efficiency. However, most prior inventions related to ammonia electrolysis have simply utilized the activity of metal catalysts, such as the development of gold-platinum mixed catalysts, photoreaction-based hydrogen production, and use as electrochemical ammonia electrolysis catalysts.

[0004] [Prior Art Literature]

[0005] [Patent Document]

[0006] Republic of Korea Patent Publication No. 2160870.

[0007] The present invention provides a hybrid electrode including plasmonic nanoparticles and an electrolytic system including the same.

[0008] However, the problems that the present invention seeks to solve are not limited to the problems mentioned above, and other problems not mentioned will be clearly understood by those skilled in the art from the description below.

[0009] The first aspect of the present invention 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 being excited by a plasmon phenomenon of the plasmonic nanoparticles are transferred to the catalyst layer.

[0010] The second aspect of the present invention provides an electrolytic 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 solution including a substance to be electrolyzed, wherein the hybrid electrode serves as an anode electrode where an oxidation reaction of the substance to be electrolyzed occurs, and electrons excited by a plasmon phenomenon of the plasmonic nanoparticles are transferred to the catalyst layer to remove an oxidation reaction intermediate from the catalyst layer.

[0011] A third aspect of the present invention provides an electrolysis method, comprising: supplying power to an electrolysis system according to the second aspect, irradiating light; and obtaining H2 from the cathode electrode.

[0012] The fourth aspect of the present invention 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 serves as an anode electrode where an oxidation reaction of a fuel occurs, and electrons excited by a plasmon phenomenon of the plasmonic nanoparticles are transferred to the catalyst layer to remove an oxidation reaction intermediate from the catalyst layer.

[0013] The hybrid electrode and electrolytic system including the same according to the embodiments of the present invention may reactivate the catalyst surface by utilizing the plasmonic phenomenon during an electrochemical reaction using a plasmonic-active electrode (antenna-reactor) composite electrode.

[0014] The electrolytic system according to the embodiments of the present invention can improve the activity and lifespan of an electrode by transferring electrons generated by plasmonic excitation of plasmonic nanoparticles to a catalyst layer and removing oxidation reaction intermediates from the catalyst layer.

[0015] Figures 1a to 1f illustrate a schematic diagram of a synthesis process of a deposited Pt(reactor)-Au(antenna) catalyst in one embodiment of the present invention (a); an XRD pattern of each electrode including a Ti fiber felt, Pt on the Ti felt, and Pt-Au on the Ti felt (b); an SEM image of Pt on the Ti felt (c and d); and an SEM image of Pt-Au on the Ti felt (e and f) (the inset in f indicates the atomic ratio of each element in the SEM-EDS profile).

[0016] Figures 2a to 2h are a schematic diagram of the electrolytic system in one embodiment of the present invention (2a); Ex-situ XANES profiles and corresponding k of Pt L3-edge extended XAFS (EXAFS) spectra for ex-situ (2b and 2c), in-situ (2d and 2e), and operando conditions (2g and 2h). 3 -weighted Fourier transform (FT) (inset is enlarged pre-edge XANES region); and k at -0.2 V and -0.2 V under plasmonic excitation conditions. 3 -The wavelet transform (WT) (2f) for the weighted EXAFS spectrum is shown.

[0017] Figures 3a to 3i are cyclic voltammetry (CV) profiles (3a) measured at a Pt-Au electrode in 1 M KOH and 0.5 M NH4OH with and without light irradiation at room temperature using an H-type cell in one embodiment of the present invention; 1 mA cm with and without light irradiation. -2 Chronopotentiometry at a constant current density (3b); CV profile after short-term stability measurement (3c); electrochemical double layer capacitance (C dl ) (3d); Peak current density with peak potential under dark or light irradiation conditions for each electrode (3e); ECSA normalized peak current density for Pt and Pt-Au electrodes (3f); Specific activity at various applied potentials (3g and 3h); and plasmonic enhancement of ammonia oxidation activity (3i).

[0018] Figures 4a to 4c show, in one embodiment of the present invention, the surface temperature of the electrode according to the light irradiation intensity (4a); the ammonia electrolysis current density stability result (4b) only through the presence or absence of light irradiation and the control of the electrolyte temperature; and the ammonia electrolysis current density stability result (4c) according to the light irradiation intensity (the ammonia electrolysis driving condition is -0.2 V vs. Ag / AgCl).

[0019] Figures 5a to 5d show, in one embodiment of the present invention, the electrochemical double layer capacitance (C) of the electrode surface when there is no light irradiation (5a), when the electrolyte temperature is increased (5b), and when there is light irradiation (5c) using an H-type cell. dl ) is the result of analyzing; and the result of calculating the amount of electrochemical double layer capacitance is (5d) (which shows that the electrochemical surface area is the highest under light irradiation conditions).

[0020] Figures 6a to 6f show, in one embodiment of the present invention, a continuous ammonia oxidation reaction (AOR) process (6a) at a constant potential of -0.2 V versus the reference electrode Ag / AgCl under dark, temperature control, and plasmon excitation conditions; the amount of NH3 reacted during the continuous AOR process in the dark and in the light (6b); the amount of NH3 reacted during the redox AOR and the continuous AOR process under light irradiation (6c); a cycling profile (6d); a durability profile including the oxidation kinetics for AOR and the total amount of NH3 reacted (6e); and the charge consumed for oxidation and reduction (Q Ox. and Q Red. ) shows the difference and ratio (6f).

[0021] Hereinafter, with reference to the attached drawings, implementation examples and embodiments of the present invention will be described in detail so that those skilled in the art can easily practice the present invention. However, the present invention may be implemented in various different forms and is not limited to the implementation examples and embodiments described herein. In addition, in the drawings, parts irrelevant to the description have been omitted to clearly explain the present invention, and similar parts have been designated with similar drawing reference numerals throughout the specification.

[0022] Throughout this specification, when a part is said to be "connected" to another part, this includes not only cases where it is "directly connected" but also cases where it is "electrically connected" with another element in between.

[0023] Throughout this specification, when it is said that an element is "on" another element, this includes not only cases where the element is in contact with the other element, but also cases where another element exists between the two elements.

[0024] Throughout this specification, whenever a part is said to "include" a component, this does not mean that it excludes other components, but rather that it may include other components, unless otherwise specifically stated.

[0025] The terms "about," "substantially," and the like used in this specification are used in a meaning that is at or close to the numerical value when manufacturing and material tolerances inherent in the meanings mentioned are presented, and are used to prevent unscrupulous infringers from unfairly exploiting the disclosure in which exact or absolute values ​​are mentioned to aid understanding of the present application.

[0026] The terms “step of ~” or “step of ~” as used throughout this specification do not mean “step for ~.”

[0027] Throughout this specification, the term "combination(s) thereof" included in the expressions in the Makushi format means one or more mixtures or combinations selected from the group consisting of the components described in the expressions in the Makushi format, and means including one or more selected from the group consisting of said components.

[0028] Throughout this specification, references to “A and / or B” mean “A or B, or A and B.”

[0029] Below, the implementation examples of the present invention are described in detail, but the present invention may not be limited thereto.

[0030] The first aspect of the present invention 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 being excited by a plasmon phenomenon of the plasmonic nanoparticles are transferred to the catalyst layer.

[0031] In one embodiment of the present invention, the substrate may be used without limitation as long as it is used as a substrate for an electrode in the relevant industry, and non-limiting examples thereof include carbon-based materials; metals including Ti, Ni, or Cu; inorganic oxides including oxides such as Ti, Zr, Al, or Si; or perovskite oxides and zeolites.

[0032] In one embodiment of the present invention, the carbon-based material may include one or more selected from graphite, carbon fiber, carbon sheet, carbon black, carbon nanotube (CNT), carbon sphere, carbon ribbon, fullerene, active carbon, carbon nanowire, and graphene, but may not be limited thereto.

[0033] In one embodiment of the present invention, the substrate may be in a form including an empty space through which a fluid passes, but may not be limited thereto.

[0034] In one embodiment of the present invention, the substrate may be in the form of a mesh structure, but may not be limited thereto.

[0035] In one embodiment of the present invention, the substrate may be formed of Ti fibers, Ni fibers, or Pt fibers in a mesh structure, but may not be limited thereto.

[0036] In one embodiment of the present invention, the catalyst layer may include one or more selected from Pt, Pd, Ir, Ag, Ru, Ni, Cu, Mn, Co, Fe, and alloys thereof, but may not be limited thereto.

[0037] In one embodiment of the present invention, the plasmonic nanoparticles may include one or more selected from Au, Ag, Pt, Pd, Rh, Re, Cu, Al, Mg, In, Ga, Ni, and Rb, but may not be limited thereto.

[0038] In one embodiment of the present invention, the diameter distribution of the plasmonic nanoparticles may be from about 5 nm to about 140 nm, and the number of the plasmonic nanoparticles having a diameter of from about 40 nm to about 90 nm may be at least about 50% of the total number of the plasmonic nanoparticles.

[0039] In one embodiment of the present invention, the diameter of the plasmonic nanoparticles may vary depending on the light irradiation conditions (light wavelength or light type, etc.) when driving the hybrid electrode and / or the type of the plasmonic nanoparticles. In one embodiment of the present invention, as a structural design capable of increasing surface plasmonic efficiency under actual solar irradiation conditions (1 Sun), the average diameter of the plasmonic nanoparticles may be about 60 nm to about 80 nm.

[0040] The second aspect of the present invention provides an electrolytic 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 solution including a substance to be electrolyzed, wherein the hybrid electrode serves as an anode electrode where an oxidation reaction of the substance to be electrolyzed occurs, and electrons excited by a plasmon phenomenon of the plasmonic nanoparticles are transferred to the catalyst layer to remove an oxidation reaction intermediate from the catalyst layer.

[0041] Detailed explanations of parts that overlap with the first aspect of the present application have been omitted, but the contents described in the first aspect of the present application may be equally applied even if the explanation is omitted in the second aspect of the present application.

[0042] In one embodiment of the present invention, the electrolytic target material may include NH3 or H2O.

[0043] In one embodiment of the present invention, when the electrolytic target substance is NH3, the electrolyte may contain ammonia water.

[0044] In one embodiment of the present invention, when the electrolytic target substance is NH3, the concentration may be about 0.1 M to about 10 M, but may not be limited thereto. In one embodiment of the present invention, when the electrolytic target substance is NH3, the concentration may be about 0.1 M to about 10 M, about 0.1 M to about 5 M, about 0.1 M to about 3 M, about 0.1 M to about 2 M, about 0.3 M to about 10 M, about 0.3 M to about 5 M, about 0.3 M to about 3 M, about 0.3 M to about 2 M, about 0.5 M to about 10 M, about 0.5 M to about 5 M, about 0.5 M to about 3 M, or about 0.5 M to about 2 M, but may not be limited thereto.

[0045] In one embodiment of the present invention, the electrolyte may further include an electrolyte comprising an alkali hydroxide.

[0046] In one embodiment of the present invention, the alkali hydroxide may include at least one selected from KOH, NaOH, and Ca(OH)2, but may not be limited thereto.

[0047] In one embodiment of the present invention, the concentration of the alkali hydroxide may be from about 0.1 M to about 10 M, but may not be limited thereto.

[0048] In one embodiment of the present invention, when the electrolytic target substance in the electrolytic system is NH3, an ammonia oxidation reaction may occur at the anode electrode to form nitrogen gas and water, and a water reduction reaction may occur at the cathode electrode to form hydrogen gas. In this case, the reaction formulas at the anode electrode and the cathode electrode are as follows:

[0049] Anode electrode: 2NH3+ 6OH - → N2+ 6H2O + 6e -

[0050] Cathode electrode: 6H2O + 6e - → 3H2+ 6OH -

[0051] In one embodiment of the present invention, when the electrolytic target material in the electrolytic system is NH3, continuous nitrogen oxide (NO) is formed on the catalyst layer due to the strong N bond that occurs at the anode electrode. x ) intermediates may be generated, resulting in a poisoning phenomenon. The nitrogen oxides may block the catalytically active surface, thereby causing a decrease in the catalytic activity of the electrode. The electrolytic system according to the embodiments of the present disclosure can improve the activity and life of the electrode by allowing electrons generated by the plasmon excitation of the plasmonic nanoparticles to be transferred to the catalyst layer, thereby removing nitrogen oxide intermediates from the catalyst layer.

[0052] In one embodiment of the present invention, the electrolytic system may further include a reference electrode. In one embodiment of the present invention, the reference electrode may include, but is not limited to, an Ag / AgCl (silver / silver chloride) electrode.

[0053] In one embodiment of the present invention, the electrolytic system may additionally include a separator.

[0054] In one embodiment of the present invention, the electrolytic system may be formed as a structure including an anode electrode part including the hybrid electrode, a cathode electrode part including the cathode electrode, a separator, a first electrolyte included in the anode electrode part, and a second electrolyte included in the cathode electrode part by additionally including a separator, and may be capable of separate production of hydrogen and nitrogen gases.

[0055] In one embodiment of the present invention, the electrolytic system may additionally include a light irradiation unit.

[0056] In one embodiment of the present invention, light having a wavelength of about 200 nm to about 2500 nm may be irradiated by the light irradiation unit.

[0057] In one embodiment of the present invention, the electrolysis system may additionally include a power supply unit.

[0058] A third aspect of the present invention provides an electrolysis method, comprising: supplying power to an electrolysis system according to the second aspect, irradiating light; and obtaining H2 from the cathode electrode.

[0059] Detailed descriptions of overlapping parts with the first and second aspects of the present application have been omitted, but the contents described for the first and second aspects of the present application may be equally applied even if the description is omitted in the third aspect of the present application.

[0060] In one embodiment of the present invention, the plasmonic phenomenon (localized surface plasmon resonance (LSPR)) of the plasmonic nanoparticles appears by the light irradiation, and the excited electrons generated at this time can escape the oxidation reaction intermediate, thereby preventing the poisoning phenomenon.

[0061] In one embodiment of the present invention, the light irradiation may be irradiating light having a wavelength of about 200 nm to about 2500 nm.

[0062] The fourth aspect of the present invention 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 serves as an anode electrode where an oxidation reaction of a fuel occurs, and electrons excited by a plasmon phenomenon of the plasmonic nanoparticles are transferred to the catalyst layer to remove an oxidation reaction intermediate from the catalyst layer.

[0063] Detailed explanations of parts that overlap with the first aspect of the present application have been omitted, but the contents described in the first aspect of the present application may be equally applied even if the explanation is omitted in the fourth aspect of the present application.

[0064] The fuel cell of the present invention may include, without limitation, a fuel cell to which the technical features of the present invention can be applied among currently commonly used fuel cells.

[0065] In one embodiment of the present invention, the fuel cell may be a hydrogen fuel cell.

[0066] In one embodiment of the present disclosure, the fuel cell may be a polymer electrolyte membrane fuel cell (PEMFC). Generally, when the fuel of the fuel cell includes C (carbon) such as natural gas, CO (carbon monoxide), which is an oxidation reaction intermediate, is generated according to the oxidation reaction of the natural gas, and the CO may be adsorbed on the catalyst layer of the anode electrode, thereby causing a poisoning phenomenon that reduces the performance of the fuel cell. The fuel cell according to the embodiments of the present disclosure can prevent the poisoning phenomenon by having electrons excited by the plasmon phenomenon of the plasmonic nanoparticles and generated be transferred to the catalyst layer, thereby removing CO from the catalyst layer.

[0067] Hereinafter, the present invention will be described in more detail using examples. However, the following examples are provided only to help understand the present invention, and the contents of the present invention are not limited to the following examples.

[0068] <Example 1: Fabrication of a hybrid electrode including a plasmonic antenna (Au) and an ammonia oxidation reactor (Pt)>

[0069] A mesh-structured substrate was fabricated using Ti fibers. Subsequently, Pt was deposited on the Ti fibers through electrodeposition, and Au nanostructures were supported thereon to fabricate a hybrid electrode comprising a plasmonic antenna (Au) and an ammonia oxidation reactor (Pt) (Fig. 1a).

[0070] The detailed process of Pt electrodeposition is as follows:

[0071] 1) A batch-type three-electrode electrochemical system was constructed.

[0072] - Ti electrode (working electrode)

[0073] - Ag / AgCl electrode (reference electrode)

[0074] - Graphite electrode (counter electrode)

[0075] 2) The electrode was immersed in 5 mM H2PtCl6 electrolyte.

[0076] 3) Pt was deposited using a cyclic voltammetry method for 100 cycles at a rate of 100 mV / s in the range of -1.0 V to -0.2 V (vs. Ag / AgCl electrode).

[0077] The detailed process of depositing Au on Pt is as follows:

[0078] 1) A three-electrode electrochemical system in the form of a batch was constructed.

[0079] - Pt on Ti electrode (working electrode)

[0080] - Ag / AgCl electrode (reference electrode)

[0081] - Graphite electrode (counter electrode)

[0082] 2) The electrode was immersed in 1 mM HAuCl4+ 0.05 M PBS electrolyte.

[0083] 3) Au was deposited using 80 cycles of cyclic voltammetry at a rate of 50 mV / s in the range of -0.855 V to -0.055 V (vs. Ag / AgCl electrode).

[0084] Referring to Fig. 1b, it can be confirmed that Pt and Au are deposited on a Ti substrate. Referring to Fig. 1c to f, the average diameter of the Au nanoparticles is approximately 70 nm, and the diameter distribution ranges from a minimum of 5 nm to a maximum of 140 nm.

[0085] <Example 2: Manufacturing of an ammonia electrolysis system including a hybrid electrode>

[0086] An ammonia electrolysis system was fabricated, comprising the hybrid electrode fabricated in Example 1 as a working electrode, a graphite electrode as a counter electrode, a Ag / AgCl electrode as a reference electrode, and an electrolyte containing ammonia water (Fig. 2a). The electrolysis system was made of PTFE (polytetrafluoroethylene) material that does not chemically react with the electrolyte. The electrolyte additionally contained KOH (1 M) electrolyte and 0.5 M NH4OH. In addition, light (1 SUN) was irradiated on the hybrid electrode to induce plasmonic activity of the hybrid electrode.

[0087] [Experimental Example]

[0088] 1. Electrochemical analysis of ammonia electrolysis reaction (plasmonic phenomenon)

[0089] In the ammonia electrolysis system of Example 2, an electrochemical analysis of the ammonia electrolysis reaction was performed depending on the presence or absence of light irradiation. Referring to Figures 3a to 3i, it was confirmed that the ammonia electrolysis reaction was improved before and after the plasmonic phenomenon. In the case of the stability test of Figure 3b, a constant constant current (1 mA cm -2) conditions, it was confirmed that the stability and efficiency were improved by the shaded portion. In the case of the cyclic voltammogram test of Fig. 3c, it was confirmed that the improvement effect of the ammonia electrolysis performance based on the plasmonic phenomenon was maintained even after the stability test of the electrode. The cyclic voltammogram of Figs. 3a and 3c was performed over a scan range of -0.9 V to 0.8 V (vs. Ag / AgCl) and a voltage of 20 mVs -1 The electrochemical reaction was measured at a scan rate of . In addition, referring to FIGS. 3d to 3f, in the case of a simple Ti support or a Pt electrode on which a Pt component is electrodeposited, the increase in electrochemical double layer capacitance and ammonia electrolysis degree was minimal under light irradiation conditions, whereas the plasmonic phenomenon occurred only when Au nanoparticles were additionally supported on the surface of the Pt electrode.

[0090] 2. Confirmation of plasmonic phenomena

[0091] Confirmation of plasmonic phenomena (temperature change)

[0092] When the plasmonic phenomenon was expressed, the change in electrode surface temperature according to the intensity of light irradiation was confirmed (Fig. 4a). A comparison of stability tests performed when the electrolyte temperature was simply increased and when the plasmonic phenomenon was induced revealed that the stability change in the ammonia electrolysis system with the simple electrolyte temperature increase was minimal (Fig. 4b). It was confirmed that the ammonia electrolysis process based on the plasmonic phenomenon improved the reaction stability of the electrode (Fig. 4c). Through this, it was confirmed that the increase in electrode surface temperature due to light irradiation was not the factor that improved the ammonia electrolysis activity and stability, but rather that the electrons induced by the plasmonic phenomenon through light irradiation were the cause of the improvement in ammonia electrolysis activity and stability.

[0093] Confirmation of plasmonic phenomena (confirmation of electrical surface area)

[0094] When plasmonic phenomena were expressed, the electrical surface area and active sites of the electrode were confirmed to be enhanced (Figures 5a to 5d). In the case of electrodes in which the electrolyte temperature was simply increased, there was no change in the electrochemical surface area. This confirmed that the increased ammonia electrolysis activity and stability upon plasmonic phenomena were the result of enhanced electrode-electrolyte interaction through increased electrochemical double-layer capacitance.

[0095] 3. Ammonia electrolysis reaction surface analysis (confirmation of surface reactivation)

[0096] Using real-time surface analysis, we confirmed through real-time and static analyses that when the plasmonic phenomenon occurred in an actual ammonia electrolysis reaction, the Pt-N bonds on the hybrid electrode surface decreased (Figs. 2b to 2h). Through this, we confirmed that the plasmonic phenomenon directly played a role in restoring the active site of the Pt electrode. Through Figs. 2b, 2d, and 2g, we determined the change in the oxidation number of the Pt metal before and after the plasmonic phenomenon, and through Figs. 2c, 2e, and 2h, we confirmed the Pt metal surface bonds before and after the plasmonic phenomenon. In particular, through the results of Figs. 2d and 2e, we confirmed that the Pt-N bonds generated during ammonia electrolysis decreased after the plasmonic phenomenon (light irradiation), thereby reconfirming that the result of the improvement in ammonia electrolysis activity and stability through the plasmonic phenomenon was the result of suppressing surface Pt-N (poisoning phenomenon). Through the results of Figure 2f, the degree of change in the Pt surface before and after the plasmonic phenomenon was visually identified.

[0097] 4. Optimization of the plasmonics-based ammonia electrolysis process (plasmonics + electrochemistry)

[0098] When the plasmonics-based oxidation / reduction protocol was performed, it was confirmed that approximately 12 times more ammonia was electrolyzed in the same amount of time compared to simple ammonia electrolysis operation (Figs. 6a to 6f). In the case of Fig. 6a, the stability of ammonia electrolysis was confirmed to increase under plasmonic and constant current conditions. Furthermore, when the plasmonic phenomenon-based oxidation (-0.2 V vs. Ag / AgCl, 60 s) and reduction (-0.8 V vs. Ag / AgCl, 6 s) condition protocol was applied, the ammonia electrolysis conditions were confirmed to be approximately 12 times higher than the ammonia electrolysis stability results under constant current conditions (Fig. 6c). Through this, stable redox activity was confirmed up to approximately 500 cycles during the redox protocol (Fig. 6d). As a result, 4.3 mmol NH3h was electrolyzed for approximately 40 hours. -1 cm 2 A plasmonic-based ammonia electrolysis protocol was confirmed to stably proceed with the ammonia electrolysis process at an electrolysis rate of .

[0099] The above description of the present invention is for illustrative purposes only, and those skilled in the art will readily appreciate that the present invention can be readily modified into other specific forms without altering the technical spirit or essential characteristics of the present invention. Therefore, the embodiments described above should be understood as illustrative in all respects and not restrictive. For example, each component described as a single entity may be implemented in a distributed manner, and similarly, components described as distributed may be implemented in a combined manner.

[0100] The scope of the present invention is indicated by the claims described below rather than the detailed description above, and all changes or modifications derived from the meaning and scope of the claims and their equivalent concepts should be interpreted as being included in the scope of the present invention.

Claims

1. Description; A catalyst layer formed on the above substrate; and Plasmonic nanoparticles formed on the above catalyst layer As a hybrid electrode including, A hybrid electrode in which electrons generated by the plasmon phenomenon of the above plasmonic nanoparticles are excited and transferred to the catalyst layer.

2. In paragraph 1, The above description is a hybrid electrode having a form including an empty space through which a fluid passes.

3. In paragraph 1, A hybrid electrode, wherein the catalyst layer comprises at least one selected from Pt, Pd, Ir, Ag, Ru, Ni, Cu, Mn, Co, Fe, and alloys thereof.

4. In paragraph 1, A hybrid electrode, wherein the plasmonic nanoparticles include at least one selected from Au, Ag, Pt, Pd, Rh, Re, Cu, Al, Mg, In, Ga, Ni, and Rb.

5. In paragraph 1, A hybrid electrode wherein the diameter distribution of the plasmonic nanoparticles is 5 nm to 140 nm, and the number of the plasmonic nanoparticles having a diameter of 40 nm to 90 nm is 50% or more of the total number of the plasmonic nanoparticles.

6. In paragraph 1, A hybrid electrode, wherein the average diameter of the above plasmonic nanoparticles is 60 nm to 80 nm.

7. A hybrid electrode comprising a substrate, a catalyst layer formed on the substrate, and plasmonic nanoparticles formed on the catalyst layer; a cathode electrode; and an electrolyte solution comprising a substance to be electrolyzed. As an electrolytic system including, The above hybrid electrode is an anode electrode where an oxidation reaction of the electrolytic target material occurs, An electrolytic system in which electrons generated by the plasmon phenomenon of the above plasmonic nanoparticles are transferred to the catalyst layer and cause oxidation reaction intermediates to be removed from the catalyst layer.

8. In paragraph 7, An electrolysis system wherein the electrolysis target substance includes NH3 or H2O.

9. In paragraph 7, An electrolysis system in which the above electrolysis target substance is NH3 and the concentration is 0.1 M to 10 M.

10. In paragraph 7, An electrolytic system, wherein the electrolyte further comprises an electrolyte containing an alkali hydroxide.

11. In paragraph 7, An electrolytic system, wherein the electrolytic system further includes a light irradiation unit.

12. In paragraph 7, The electrolytic system further comprises a power supply unit.

13. A hybrid electrode comprising a substrate, a catalyst layer formed on the substrate, and plasmonic nanoparticles formed on the catalyst layer; a cathode electrode; and an electrolyte layer. As a fuel cell, including: The above hybrid electrode is an anode electrode where the oxidation reaction of the fuel occurs. A fuel cell in which electrons generated by the plasmon phenomenon of the above plasmonic nanoparticles are transferred to the catalyst layer and cause oxidation reaction intermediates to be removed from the catalyst layer.

14. In paragraph 13, Hydrogen fuel cell, fuel cell.

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