WO2020218875A1 - Catalyseur bifonctionnel à base de nanoagrégats de nickel pour des réactions d'évolution d'oxygène et d'hydrogène et procédé pour sa production - Google Patents

Catalyseur bifonctionnel à base de nanoagrégats de nickel pour des réactions d'évolution d'oxygène et d'hydrogène et procédé pour sa production Download PDF

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WO2020218875A1
WO2020218875A1 PCT/KR2020/005438 KR2020005438W WO2020218875A1 WO 2020218875 A1 WO2020218875 A1 WO 2020218875A1 KR 2020005438 W KR2020005438 W KR 2020005438W WO 2020218875 A1 WO2020218875 A1 WO 2020218875A1
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pet
nickel
oxygen
nanocluster
catalyst
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Korean (ko)
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이동일
곽규주
최우준
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연세대학교 산학협력단
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/22—Organic complexes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/90—Selection of catalytic material
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells

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  • the present invention relates to a nickel nanocluster bifunctional catalyst for oxygen and hydrogen generation reaction, and a method for producing the same.
  • a nanocluster or superatom composed of a certain number of metal atoms and ligands follows the macroatomic orbital theory, in which the valence electrons of the particles are newly defined, and this is considered to be one giant atom. It is a theory.
  • Nanoclusters are stable compared to one atom or nanoparticles, and have strong molecular properties than metallic properties, and thus have optical and electrochemical properties that are completely different from nanoparticles.
  • optical, electrical and catalytic properties of nanoclusters are sensitively changed depending on the number of metal atoms, types of metal atoms, and ligands, research on nanoclusters is actively in progress in a wide variety of fields.
  • Alkaline water electrolysis consists of a hydrogen evolution reaction (HER) and an oxygen evolution reaction (OER), among which relatively slow OER activity needs to be improved.
  • HER hydrogen evolution reaction
  • OER oxygen evolution reaction
  • ruthenium (Ru)-based catalysts are the most excellent in OER activity, but have a disadvantage of poor stability, and thus, catalysts are being commercialized centering on relatively stable iridium (Ir)-based catalysts.
  • the iridium (Ir)-based catalyst has a high price, a limited reserve, and a low uniformity, there is a need to develop a catalyst having excellent oxygen generation reaction activity that can replace it.
  • Korean Patent Publication No. 10-1854184 is proposed as a similar prior document.
  • the present invention has excellent stability compared to a ruthenium (Ru)-based catalyst, and is cheaper than an iridium (Ir)-based catalyst, and has excellent uniformity, and a nickel nanocluster dual-functional catalyst for oxygen and hydrogen generation reactions. It is an object of the present invention to provide, and a manufacturing method thereof.
  • the present invention provides a nickel nanocluster bifunctional catalyst for carbon dioxide conversion reaction satisfying Formula 1 above.
  • One aspect of the present invention relates to a nickel nanocluster bifunctional catalyst for oxygen and hydrogen evolution, satisfying the following formula (1).
  • SR is an organothiol-based ligand.
  • the organothiol-based ligand of Formula 1 may be (C6-C12)aryl (C1-C10)alkylthiol.
  • another aspect of the present invention is a) preparing a reaction solution by reacting a nickel precursor and a catalyst in the presence of a solvent; And b) adding an organic thiol-based ligand compound and a reducing agent to the reaction solution to synthesize a nickel nanocluster satisfying the following formula (1); comprising, a method for producing a nickel nanocluster bifunctional catalyst for oxygen and hydrogen generation reactions It is about.
  • SR is an organothiol-based ligand.
  • the molar concentration of the nickel precursor may be 10 mM or less
  • the time interval for adding the organic thiol-based ligand compound and the reducing agent may be 5 minutes or less
  • the solvent of the step may be a polar aprotic solvent having a dielectric constant of 30 to 50, and specifically, the polar aprotic solvent is any selected from the group consisting of dimethylformamide (DMF) and dimethyl sulfoxide (DMSO). It may be one or more than one.
  • the present invention provides a nickel nanocluster bifunctional catalyst for carbon dioxide conversion reaction satisfying Formula 1 above.
  • the nickel nanocluster bifunctional catalyst for oxygen and hydrogen generation reaction in which 41 nickel atoms and 25 organic thiol-based ligands are bonded in a specific structure according to the present invention has excellent activity against oxygen and hydrogen generation reactions in solutions of all acidity.
  • it has excellent stability compared to ruthenium (Ru)-based catalysts, and is cheaper than iridium (Ir)-based catalysts and has excellent uniformity, and thus can be very useful as a catalyst for alkaline water electrolysis.
  • the method for preparing a nickel nanocluster bifunctional catalyst for oxygen and hydrogen generation reaction according to the present invention is to control the molar concentration of the nickel precursor, control the addition time interval of the compound to be added, and use a specific solvent. It is possible to effectively synthesize a nickel nanocluster in which 25 thiol-based ligands are bonded to a specific structure, and through this, there is an advantage that a nickel nanocluster bifunctional catalyst for oxygen and hydrogen generation reactions having the above effect can be provided.
  • the nickel nanocluster bifunctional catalyst for carbon dioxide conversion reaction of the present invention has very high activity in the carbon phosphate conversion reaction.
  • Ni 41 (PET) 25 Ni 6 (PET) 12
  • Ni 5 (PET) 10 Ni 4 (PET) 8 .
  • MALDI-MS Maldi mass analysis data of Ni 41 (PET) 25 and Ni 6 (PET) 12 .
  • Ni 41 (PET) 25 Ni 6 (PET) 12
  • Ni 5 (PET) 10 Ni 4 (PET) 8 nanoclusters.
  • Figure 5 is a square wave voltammogram (CV) analysis data of Ni 41 (PET) 25, Ni 6 (PET) 12 , Ni 5 (PET) 10 , and Ni 4 (PET) 8 nanoclusters, and the horizontal axis is voltage (V vs Fc +/0 ), and the vertical axis is the current (A).
  • CV chemical vapor deposition
  • FIG. 7 is data for confirming oxygen generation reactivity of nanocluster-nickel foam or IrO2-nickel foam composite films prepared in Preparation Example 1, Comparative Preparation Example 2, Comparative Preparation Example 3, Comparative Preparation Example 4, and Comparative Preparation Example 5.
  • FIG. 7 is data for confirming oxygen generation reactivity of nanocluster-nickel foam or IrO2-nickel foam composite films prepared in Preparation Example 1, Comparative Preparation Example 2, Comparative Preparation Example 3, Comparative Preparation Example 4, and Comparative Preparation Example 5.
  • Ni 41 (PET) 25 which are commercial catalysts
  • a and b of FIG. 6 are nickel foam
  • c and d are results for Ni 41 (PET) 25 .
  • FIG. 9 is a data analysis of the HER catalytic activity of Ni 41 (PET) 25 and Ni 6 (PET) 12 nanoclusters according to the acidity of the solution, in FIG. 7 a is pH 1, b is pH 3, c is pH 7 , d is the linear scanning potential analysis data in a solution of pH 14.
  • FIG. 13 shows the carbon dioxide conversion catalytic activity of Ni 41 (PET) 25 nanoclusters in an argon (Ar) or carbon dioxide (CO 2 ) environment was confirmed through a linear scanning potential method.
  • FIG. 14 is data obtained by analyzing Faraday efficiency (left, [%]) and current density (mA/cm2) using a constant voltage electrolysis method of Ni 41 (PET) 25 nanoclusters.
  • first, second, A, B, (a) and (b) may be used. These terms are only used to distinguish the component from other components, and the nature, order, or order of the component is not limited by the term.
  • Alkaline water electrolysis consists of a hydrogen evolution reaction (HER) and an oxygen evolution reaction (OER), among which relatively slow OER activity needs to be improved.
  • HER hydrogen evolution reaction
  • OER oxygen evolution reaction
  • ruthenium (Ru)-based catalysts are the most excellent in OER activity, but have a disadvantage of poor stability, and iridium (Ir)-based catalysts have limitations in that they are not only expensive, but have limited reserves and low uniformity.
  • nickel nanoclusters have superior stability compared to ruthenium (Ru)-based catalysts, and are cheaper than iridium (Ir)-based catalysts and have excellent uniformity to complete the present invention. Reached.
  • one aspect of the present invention relates to a nickel nanocluster bifunctional catalyst for oxygen and hydrogen generation reaction that satisfies the following formula (1).
  • SR is an organothiol-based ligand.
  • the nickel nanocluster bifunctional catalyst for oxygen and hydrogen generation reactions in which 41 nickel atoms and 25 organic thiol-based ligands are bonded in a specific structure may be used in the following reaction formula, and the activity for oxygen and hydrogen generation reactions is all
  • it has excellent stability compared to ruthenium (Ru)-based catalysts, and is cheaper than iridium (Ir)-based catalysts and has excellent uniformity, so that it can be very useful as a catalyst for alkaline water electrolysis.
  • the organic thiol-based ligand SR is a C1-C30 alkanthiol, a C6-C30 arylthiol, a C3-C30 cycloalcanthiol, a C5-C30 hetero It may be any one or two or more selected from the group consisting of arylthiol, heterocycloalkanethiol having 3 to 30 carbon atoms, and arylalkanethiol having 6 to 30 carbon atoms, and the organothiol-based ligand is one or more hydrogens in the functional group as a substituent.
  • the substituent is an alkyl group having 1 to 10 carbon atoms, a halogen group (-F, -Br, -Cl, -I), a nitro group, a cyano group, a hydroxy group, an amino group, and 6 to 20 carbon atoms.
  • an aryl group an alkenyl group having 2 to 7 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, a heterocycloalkyl group having 3 to 20 carbon atoms, or a heteroaryl group having 4 to 20 carbon atoms, provided that the number of carbon atoms of the organic thiol-based ligand described above is It does not include the number of carbon atoms of the substituent.
  • the alkyl group may be linear or branched.
  • the organothiol-based ligand is pentanethiol, hexanethiol, heptanethiol, 2,4-dimethylbenzenethiol, 2-phenylethanethiol, glutathione, thiopronin, thiolated poly(ethylene glycol), It may be any one or two or more selected from the group consisting of p-mercaptophenol and (r-mercaptopropyl)-trimethoxysilane), but is not limited thereto.
  • the organothiol-based ligand of the present invention may be (C6-C12)aryl (C1-C10)alkylthiol, more preferably phenyl((C1-C6)alkylthiol, for example phenylmethylthiol, It may be phenylethylthiol, 2-phenylethylthiol, 1-phenylpropylthiol, 2-phenylpropylthiol, 3-phenylpropylthiol, pentylthiol, or hexylthiol, but is not limited thereto.
  • another aspect of the present invention relates to a film for oxygen and hydrogen generation reactions comprising a nickel nanocluster bifunctional catalyst for oxygen and hydrogen generation reactions satisfying Formula 1, wherein the film for oxygen and hydrogen generation reactions Silver can be used as an electrode for oxygen and hydrogen gas generation reaction.
  • the oxygen and hydrogen generation reaction film may include a nickel nanocluster bifunctional catalyst for oxygen and hydrogen generation reactions satisfying Formula 1, a conductive material, and a polymer binder.
  • the weight ratio of the nickel nanocluster bifunctional catalyst for oxygen and hydrogen generation reaction the conductive material may be 1:0.5 to 2, preferably 1:0.8 to 1.2.
  • the oxygen and hydrogen generation reaction nickel nanocluster bifunctional catalyst When the weight ratio of the conductive material satisfies the above range, the oxygen and hydrogen generation reaction nickel nanocluster bifunctional catalyst can cover the surface of the conductive material with a single layer, so the minimum catalyst It is good that it can reduce the cost and at the same time show the maximum catalyst efficiency.
  • the conductive material may be a carbon material, but if it is commonly used in the art, it may be used without particular limitation.
  • Specific examples of the carbon body may be any one or two or more selected from the group consisting of carbon black, super-p, activated carbon, hard carbon, and soft carbon, but is not limited thereto.
  • the polymeric binder is used for solid fixation of a nickel nanocluster bifunctional catalyst for oxygen and hydrogen generation reactions and a conductive material, and if it is commonly used in the art, it may be used without particular limitation. , Specifically, it may be, for example, Nafion.
  • the amount of the polymeric binder added is not particularly limited as long as the nickel nanocluster bifunctional catalyst for oxygen and hydrogen generation reactions and the conductive material are firmly fixed, and as a specific example, a nanocluster catalyst for hydrogen gas generation:
  • the weight ratio may be 1:5 to 30, preferably 1:10 to 20, but is not limited thereto.
  • another aspect of the present invention is a) preparing a reaction solution by reacting a nickel precursor and a catalyst in the presence of a solvent; And b) adding an organic thiol-based ligand compound and a reducing agent to the reaction solution to synthesize a nickel nanocluster satisfying the following formula (1); comprising, a method for producing a nickel nanocluster bifunctional catalyst for oxygen and hydrogen generation reactions It is about.
  • SR is an organic thiol-based ligand, and SR in Chemical Formula 1 is the same as described above, and redundant descriptions are omitted.
  • the activity against oxygen and hydrogen generation reactions is excellent in all solutions of acidity, as well as ruthenium (Ru)-based catalysts. It has excellent stability compared to the iridium (Ir)-based catalyst, and is cheaper than the iridium (Ir)-based catalyst and has excellent uniformity, so that a catalyst for alkaline water electrolysis can be prepared.
  • the manufacturing method according to an embodiment of the present invention comprises 41 nickel atoms and 25 organothiol-based ligands in a specific structure by adjusting the molar concentration of the nickel precursor, adjusting the addition time interval of the compound to be added, and using a specific solvent.
  • the combined nickel nanoclusters can be effectively synthesized, and there is an advantage of providing a nickel nanocluster bifunctional catalyst for oxygen and hydrogen generation reactions having the above effects.
  • a step of preparing a reaction solution by reacting a nickel precursor and a catalyst may be performed.
  • the molar concentration of the nickel precursor may be 10 mM or less, more preferably 7 mM or less, and even more preferably 0.1 2 to 5 mM. In this range, it may be possible to synthesize a nickel cluster satisfying Formula 1.
  • the molar concentration of the nickel precursor is more than 10 mM, Ni 6 (SR) 12 is synthesized, and thus it may be difficult to synthesize the target Ni 41 (SR) 25 .
  • the nickel precursor may be used without particular limitation as long as it is commonly used in the art, and as a specific example, NiCl 2 , Ni(NO 3 ) 2 , NiSO 4 and Ni( C 5 H 7 O 2 ) It may be any one or two or more selected from the group consisting of 2 and the like, and preferably, the use of NiCl 2 is better in improving the synthesis efficiency.
  • the solvent in step a) may be a polar aprotic solvent having a dielectric constant of 30 to 50, and as a more specific example, the polar aprotic solvent is dimethylformamide ( DMF) and dimethyl sulfoxide (DMSO) may be any one or two or more selected from the group consisting of.
  • DMF dimethylformamide
  • DMSO dimethyl sulfoxide
  • Ni 6 (SR) 12 is synthesized and the target Ni 41 (SR) 25 is synthesized. It can be difficult.
  • the amount of the solvent to be added is preferably adjusted to such an extent that the nickel precursor can have an appropriate molar concentration.
  • the catalyst may be used without particular limitation as long as it is commonly used in the art, and the group consisting of tetraoctyl ammonium bromide (TOAB) and tetraphenylphosphine bromide (PPh 4 Br), etc. It may be any one or two or more selected from, preferably using tetraoctyl ammonium bromide (TOAB) is good in improving the reaction efficiency.
  • TOAB tetraoctyl ammonium bromide
  • Ph 4 Br tetraphenylphosphine bromide
  • the addition amount of the catalyst may be a nickel precursor: the molar ratio of the catalyst is 1: 0.5 to 10, more preferably 1: 1 to 5, even more preferably 1: 1.5 to 3.
  • Ni 6 (SR) 12 is synthesized, so that synthesis of the target Ni 41 (SR) 25 may be difficult.
  • the time interval for the addition of the organic thiol-based ligand compound and the reducing agent may be 5 minutes or less, more preferably 3 minutes or less, and even more preferably 1 minute or less.
  • the lower limit of the addition time interval is not particularly limited, but the minimum time it takes physically to add the reducing agent after adding the organic thiol-based ligand compound may be the lower limit of the addition time interval, specifically, for example, 5 seconds. It can be more than
  • the organothiol-based ligand compound may be RSH, which is a compound before hydrogen falls compared to the SR, and as a specific example, an alkanethiol having 1 to 30 carbon atoms and an alcanthiol having 6 to 30 carbon atoms Any one or two selected from the group consisting of arylthiol, cycloalcanthiol having 3 to 30 carbon atoms, heteroarylthiol having 5 to 30 carbon atoms, heterocycloalcanthiol having 3 to 30 carbon atoms, and arylalkanthiol having 6 to 30 carbon atoms Or more, and in the organic thiol-based ligand, one or more hydrogens in the functional group may be further substituted or unsubstituted with a substituent, wherein the substituent is an alkyl group having 1 to 10 carbon atoms, a halogen group (-F, -Br, -Cl, -I), nitro group,
  • the organothiol-based ligand is pentanethiol, hexanethiol, heptathiol, 2,4-dimethylbenzenethiol, 2-phenylethanethiol, glutathione, thiopronin, thiolated poly(ethylene glycol) , p-mercaptophenol and (r-mercaptopropyl)-trimethoxysilane) may be any one or two or more selected from the group consisting of, but is not limited thereto.
  • the organothiol-based ligand of the present invention may be (C6-C12)aryl (C1-C10)alkylthiol, more preferably phenyl((C1-C6)alkylthiol, for example phenylmethylthiol, It may be phenylethylthiol, 2-phenylethylthiol, 1-phenylpropylthiol, 2-phenylpropylthiol, 3-phenylpropylthiol, pentylthiol, or hexylthiol, but is not limited thereto.
  • the mixing ratio of the nickel precursor and the organic thiol-based ligand compound may be a ratio commonly mixed in the art, and as a specific example, the molar ratio of the nickel precursor: the organic thiol-based ligand compound is 1: It may be 1 to 15, more preferably 1: 1.5 to 10, even more preferably 1: 2 to 5. In such a range, the synthesis efficiency is excellent and reaction impurities can be reduced.
  • the reducing agent may be used without particular limitation as long as it is commonly used in the art, and as a specific example, the reducing agent may be NaBH 4 , but is not limited thereto.
  • the reducing agent may be added 5 to 30 mmol based on 1 mmol of the nickel precursor, but this is only an example and the present invention is not limited thereto.
  • an additional purification process may be further performed in order to obtain a high-purity nickel nanocluster, and the additional purification process may be performed through a conventional method.
  • the nickel nanocluster bifunctional catalyst for conversion of carbon dioxide to carbon dioxide of the present invention has very high activity in the conversion reaction of carbon dioxide.
  • Triethylamine was used instead of the reducing agent, and tetrahydrofuran (THF) was used instead of dimethyl sulfoxide (DMSO) as the reaction solvent, and all processes were carried out in the same manner as in Example 1, and high purity Ni 4 (PET) 8 was used. Obtained.
  • the prepared nanocluster-carbon black composite dispersion was solution-deposited on a 1 cm2 area of the gas diffusion type microporous carbon electrode (Effects of gas diffusion layer (GDL) and micro porous layer (MPL); GDE) to form carbon black.
  • -Nanocluster composite film Ni 41 (PET) 25 , Ni 41 /GDL was prepared.
  • Ni 41 (PET) 25 13.3 ⁇ g was added to 50 ⁇ l of tetrahydrofuran (THF) solution and ultrasonically dispersed for about 10 minutes, followed by solution deposition on nickel foam (NF) with an area of 1 cm2 and nanocluster-nickel foam
  • a composite film Ni 41 (PET) 25 -nickel foam, represented by Ni 41 /NF) was prepared.
  • FIG. 1 is an electrospray ionization mass spectrometry diagram of Ni 41 (PET) 25, Ni 6 (PET) 12 , Ni 5 (PET) 10 , and Ni 4 (PET) 8 nanoclusters, in Examples and Comparative Examples It was confirmed that the prepared Ni 41 (PET) 25, Ni 6 (PET) 12 , Ni 5 (PET) 10 , and Ni 4 (PET) 8 nanoclusters were well synthesized in a single composition.
  • Figure 4 is a UV-visible-near-infrared absorption spectrum measurement results of Ni 41 (PET) 25, Ni 6 (PET) 12 , Ni 5 (PET) 10 , and Ni 4 (PET) 8 nanoclusters, almost similar absorption wavelengths I was able to confirm that it showed.
  • Figure 5 is a square wave voltammogram (CV) analysis data of NNi 41 (PET) 25, Ni 6 (PET) 12 , Ni 5 (PET) 10 , and Ni 4 (PET) 8 nanoclusters, the horizontal axis is voltage (V vs Fc +/0 ), and the vertical axis is the current (A).
  • CV square wave voltammogram
  • the Ni 41 (PET) 25 and Ni 6 (PET) 12 nanoclusters have almost the same shape of the CV curve, but the distance between the peaks of Ni 41 (PET) 25 was further reduced. It was confirmed that the oxygen and hydrogen generation reaction activity was improved from this.
  • Ni 41 (PET) 25 - nickel foam composite electrode was found to show a higher current value at any potential relative to electrode 25 -GDE composite Ni 41 (PET). This may be due to increased dispersibility of Ni 41 (PET) 25 on the nickel foam and corrosion of the carbon material under oxidation conditions.
  • Ni 41 (PET) 25 -nickel foam electrode exhibits the highest activity, which may be due to the fact that the distance between the peaks of Ni 41 (PET) 25 is further reduced as shown in FIG. 5.
  • Ni 41 (PET) 25 -nickel foam composite electrode shows a higher OER catalytic activity than commercial iridium oxide-nickel foam.
  • FIGS. 6A and 6B are nickel foam, c and d Is the result for Ni 41 (PET) 25 .
  • FIG. 8 are analysis data of a linear scanning potential method of nickel foam and Ni 41 (PET) 25.
  • Ni 41 (PET) 25 has a higher current density and lower starting voltage than nickel foam. It was confirmed to have. Particularly, at pH 14, it was found that the iridium (Ir)-based catalyst and the initiation voltage were similar, but had a higher current density, and thus had very good OER catalyst activity.
  • Ni 41 (PET) 25 has excellent OER catalytic activity in all acidity solutions.
  • FIG. 9 is a data analysis of the HER catalytic activity of Ni 41 (PET) 25 and Ni 6 (PET) 12 nanoclusters according to the acidity of the solution, in FIG. 7 a is pH 1, b is pH 3, c is pH 7 , d is the linear scanning potential analysis data in a solution of pH 14.
  • Ni 41 (PET) 25 in the solution of all acidity had higher current density and lower starting voltage than Ni 6 (PET) 12 .
  • Table 1 below shows the results of overvoltage measurement for each catalyst using the linear scanning potential method analysis data in specific values.
  • PtAu 24 (PET) 18 the world's best HER catalyst
  • the overvoltage is at a current density of 10 Compared to 440 mV (in pH 3) and 240 mV (in pH 14)
  • the overvoltage at a current density of 10 mA/cm2 was 630 mV (in pH 3), 510 mV (in It was confirmed that pH 14) had only an increase in overvoltage of about 190 to 270 mV per acidity, and thus had excellent HER catalytic activity compared to other catalysts (Au 25 (PET) 12 and Ni 6 (PET) 12 ).
  • Ni 41 (PET) 25 showed about 80% performance compared to PtAu 24 (PET) 12 , the world's best HER catalyst, and it was confirmed that it can be used as a dual functional (OER and HER) catalyst. .
  • Table 2 shows the HER activity analysis results of the Ni 41 (PET) 25 and Ni 6 (PET) 12 nanoclusters using the linear scanning potential method analysis data of FIG. 7 as specific values, and the following overvoltage is 10 mA/ It is measured at a current density of cm2.
  • Figures 13 and 14 are experiments of the carbon dioxide conversion reactivity of the Ni 41 (PET) 25 nanoclusters
  • Figure 11 is the carbon dioxide conversion catalyst activity in an argon (Ar) or carbon dioxide (CO 2 ) environment through a linear scanning potential method
  • 12 is a data obtained by analyzing the Faraday efficiency (left, [%]) and current density (mA/cm2) using the constant voltage electrolysis method.
  • Ni 41 (PET) 25 nanoclusters are not only OER and HER, but also carbon dioxide. It was confirmed that the catalytic activity was also shown in the conversion reaction.

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Abstract

La présente invention concerne : un catalyseur bifonctionnel à base de nanoagrégats de nickel qui est destiné à des réactions d'évolution d'oxygène et d'hydrogène et dans lequel 41 atomes de nickel et 25 ligands à base d'organothiol sont liés dans une structure spécifique ; et un procédé pour sa production. La présente invention concerne un catalyseur présentant une excellente activité pour REO et des REH dans toutes les solutions acides.
PCT/KR2020/005438 2019-04-26 2020-04-24 Catalyseur bifonctionnel à base de nanoagrégats de nickel pour des réactions d'évolution d'oxygène et d'hydrogène et procédé pour sa production WO2020218875A1 (fr)

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KR1020200049410A KR102374679B1 (ko) 2019-04-26 2020-04-23 산소 및 수소 발생 반응용 니켈 나노클러스터 이중기능성 촉매, 및 이의 제조방법

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