WO2021125543A1 - Catalyseur de réaction d'évolution d'hydrogène comprenant des nanofibres d'alliage rhodium-nickel, et procédé de fabrication de nanofibres d'alliage rhodium-nickel - Google Patents

Catalyseur de réaction d'évolution d'hydrogène comprenant des nanofibres d'alliage rhodium-nickel, et procédé de fabrication de nanofibres d'alliage rhodium-nickel Download PDF

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WO2021125543A1
WO2021125543A1 PCT/KR2020/014791 KR2020014791W WO2021125543A1 WO 2021125543 A1 WO2021125543 A1 WO 2021125543A1 KR 2020014791 W KR2020014791 W KR 2020014791W WO 2021125543 A1 WO2021125543 A1 WO 2021125543A1
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rhodium
nanofibers
catalyst
nickel alloy
nickel
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English (en)
Korean (ko)
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이영미
김명화
이종목
진다솔
유아름
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이화여자대학교 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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
    • B01J23/892—Nickel and noble metals
    • 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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • 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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/005—Spinels
    • 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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
    • 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
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
    • B01J35/58—Fabrics or filaments
    • 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/08—Heat treatment
    • 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
    • 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
    • B01J37/341—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation
    • B01J37/342—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation of electric, magnetic or electromagnetic fields, e.g. for magnetic separation
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B1/00—Electrolytic production of inorganic compounds or non-metals
    • C25B1/01—Products
    • C25B1/02—Hydrogen or oxygen
    • C25B1/04—Hydrogen or oxygen by electrolysis of water
    • 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
    • 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
    • H01M4/9016—Oxides, hydroxides or oxygenated metallic salts
    • 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
    • Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
    • 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

Definitions

  • the present application relates to a catalyst for hydrogen generation reaction including a rhodium-nickel alloy nanofiber, a hydrogen energy generating device including the same, and a method for manufacturing the rhodium-nickel alloy nanofiber.
  • platinum is the best performing catalyst found so far for HER. This is because Pt can form Pt-H bonds with ideal bond strength and is strong enough to facilitate adsorption and reduction of H + , but sufficient to readily release H 2 when reduction is complete. From the factors inducing the above-mentioned catalyst stability and high electroactivity in Pt pure metal, recent studies investigated mixed metal or alloy catalysts as strategies to improve the activity and stability, suggesting the following possible factors. was set. For example, when metal A and metal B coexist to form an intermetallic alloy, the various phases may be provided as two phases or as a mixture of an intermetallic alloy having a crystal structure different from that of A and B. have.
  • the present application provides a catalyst for hydrogen generation reaction including a rhodium-nickel alloy nanofiber, a hydrogen energy generating device including the same, and a method of manufacturing the rhodium-nickel alloy nanofiber.
  • Rhodium-nickel alloy nanofibers were synthesized from a NiRh 2 O 4 single spinel phase, where the RhNi alloy is a reduced form of NiRh 2 O 4 under certain reducing conditions.
  • catalytic activity tests were performed in various pH aqueous solutions. RhNi alloy nanofibers significantly outperform Pt/C, pure Rh metal, and other previously reported Rh-based catalysts, demonstrating remarkably superior HER electroactivity with low overpotential and small Tafel gradients in all pH solutions. was shown.
  • a first aspect of the present disclosure provides a catalyst for hydrogen evolution, comprising rhodium-nickel alloy nanofibers, wherein the alloy is formed from a single spinel phase of NiRh 2 O 4 , the catalyst for hydrogen evolution reaction .
  • a second aspect of the present application provides a device for generating hydrogen energy, including the catalyst for a hydrogen evolution reaction according to the first aspect of the present application.
  • a third aspect of the present application is, (a) preparing a precursor solution by dissolving a rhodium precursor and a nickel precursor in a mixed solvent containing an alcohol and water having 1 to 5 carbon atoms; (b) electrospin the precursor solution followed by calcination to obtain a single spinel rhodium-nickel oxide nanofiber; and (c) reducing the rhodium-nickel oxide nanofibers to obtain a rhodium-nickel alloy nanofiber, rhodium-provides a method for producing a nickel alloy nanofiber.
  • the rhodium-nickel alloy nanofibers included in the catalyst for hydrogen evolution according to the embodiments of the present application were synthesized from a NiRh 2 O 4 single spinel phase, where the RhNi alloy is NiRh 2 O 4 under specific reducing conditions. It is a reduced form.
  • catalytic activity tests were performed in various pH aqueous solutions. RhNi alloy nanofibers significantly outperform Pt/C, pure Rh metal, and other previously reported Rh-based catalysts, resulting in low overpotential and small Tafel at about -10 mA cm -2 in all pH solutions. It exhibited remarkably good HER electroactivity validated as a slope.
  • the rhodium-nickel alloy nanofiber according to the present application has an AC impedance of 5 ⁇ to 15 ⁇ in all pH ranges and thus has remarkably excellent conductivity.
  • the HER activity of the catalyst for hydrogen evolution according to the embodiments of the present application is superior to that of pure metals Rh and Ni, and even Pt/C, with sufficiently large current density and smaller Tafel gradient under all-pH conditions. .
  • rhodium-nickel alloy nanofibers as catalysts for hydrogen evolution (HEC) showed good electrochemical activity in all-pH media, where HEC was not commonly reported in all-pH media.
  • the catalyst for hydrogen evolution reaction according to the embodiments of the present application hardly changed the potential to generate about 10 mA ⁇ cm -2 for about 1,000 repeated scans in all-pH medium. That is, the catalyst for hydrogen evolution according to the embodiments of the present application not only has a catalytic activity comparable to Pt/C at low overpotential and high current density, but also at an actual working potential that produces about 10 mA cm -2 It supports stability for about 1,000 repeated cycles.
  • a rhodium-nickel oxide on a single spinel specifically NiRh 2 O 4
  • a rhodium-nickel alloy nanofiber can be prepared from, the present application Rhodium-nickel oxide prepared using a precursor solution prepared by dissolving a rhodium precursor and a nickel precursor in a mixed solvent containing an alcohol and water having 1 to 5 carbon atoms mixed according to a certain ratio is not a mixture or a composite. obtained in a single phase. Accordingly, since the rhodium-nickel alloy nanofiber can also be obtained as a single phase, a separate purification process and/or separation process is not required.
  • FIG. 1 is a schematic diagram of a method of manufacturing a rhodium-nickel alloy nanofiber according to embodiments of the present application.
  • 2(a) to 2(d) are SEM images of single-phase nanofibers of (a) NiRh 2 O 4 , (b) RhNi@200° C., (c) Rh metal, and (d) Ni metal, respectively. admit.
  • FIGS. 3(a) to 3(g) are images related to the characteristic analysis of NiRh 2 O 4
  • FIGS. 3(h) to 3(m) are images related to the characteristic analysis of RhNi@200°C.
  • FIGS. 3(a) and 3(h) are low-magnification TEM images, respectively
  • FIGS. 3(b) and 3(i) are high-resolution TEM images, respectively
  • FIGS. 3(c) and 3( j), respectively are Fast Fourier transform (FFT) images of the lattice decomposition image
  • FIGS. 3(d) and 3(k) are HADDF-STEM (High-angle annular dark-field STEM) images, respectively.
  • FFT Fast Fourier transform
  • FIGS. 3(e), 3(f), and 3(g) are the corresponding elemental mapping analysis images of Rh, Ni and O in NiRh 2 O 4 , respectively, and FIGS. 3(l) and 3 (m) are the corresponding elemental mapping analysis images of Rh and Ni at RhNi@200°C, respectively.
  • NiRh 2 O 4 is an XRD pattern of Rh, Ni, RhNi@200° C., NiRh 2 O 4 , and reference NiRh 2 O 4 (JCPDS 73-1040).
  • 5(a) to 5(d) are, respectively, (a) NiRh 2 O 4 , and (b) XPS spectra of RhNi@200°C nanofibers, NiRh 2 O 4 , and RhNi@200°C nanofibers. (c) high-resolution Rh 3d XPS spectrum and (d) high-resolution Ni 2p XPS spectrum.
  • 6(a) to 6(f) are polarization curves using iR correction of NiRh 2 O 4 , RhNi@200° C., Rh, Ni, and Pt/C, respectively, N 2 -saturation (a) 1 M RDE voltammograms for HER at a current density of 10 mV s ⁇ 1 with a rotational speed of 1,600 rpm in NaOH, (b) 1 M PBS, and (c) 1 M HClO 4 aqueous solution, The corresponding Tafel plots of (d), (e), and (f) for RDE were obtained from the RDE voltage-current curves shown in (a), (b), and (c), respectively.
  • FIGS. 8(d) to 8(f) are, respectively, FIG. 8(a) to 8(c) are graphs showing potentials that generate 10 mA ⁇ cm -2 for every 100 scans corresponding to the polarization curves, respectively.
  • FIG. 9 is XRD data when rhodium-nickel oxide, which is a material before reduction of a rhodium-nickel alloy, is a composite oxide rather than a single phase.
  • step of doing or “step of” does not mean “step for”.
  • RhNi@T°C represents RhNi nanofibers after thermal annealing at the temperature (T) of reducing conditions.
  • a first aspect of the present disclosure provides a catalyst for hydrogen evolution, comprising rhodium-nickel alloy nanofibers, wherein the alloy is formed from a single spinel phase of NiRh 2 O 4 , the catalyst for hydrogen evolution reaction .
  • the single spinel phase of NiRh 2 O 4 may be simply denoted as AB 2 X 4 .
  • the alloy can be obtained by the reduction of a single spinel phase of the NiRh 2 O 4, the NiRh 2 O 4 If a composite oxide (composite oxide), which is several different blend not on the single spinel of the NiRh The material after reduction of 2 O 4 can also be obtained as a composite. Therefore, in order to prepare the rhodium-nickel bimetallic alloy of the present application, the NiRh 2 O 4 before reduction must be a single spinel phase.
  • the alloy may have a tensile lattice strain by embedding the nickel in the cubic lattice of rhodium.
  • the hydrogen generation reaction may include an electrolysis reaction of water, but may not be limited thereto.
  • the diameter of the nanofiber may be about 100 nm to about 250 nm, but may not be limited thereto.
  • the nanofiber has a diameter of about 100 nm to about 250 nm, about 100 nm to about 240 nm, about 100 nm to about 230 nm, about 100 nm to about 220 nm, about 100 nm to about 210 nm, about 100 nm to about 200 nm, about 100 nm to about 190 nm, about 100 nm to about 180 nm, about 100 nm to about 170 nm, about 100 nm to about 160 nm, about 100 nm to about 150 nm, about 100 nm to about 140 nm, about 100 nm to about 130 nm, about 100 nm to about 120 nm, about 100 nm to about 110 nm, about 120 nm to about 250 nm, about 120 nm to about 240
  • the catalyst for hydrogen generation reaction may have an overpotential of about -0.01 V to about -0.05 V at a current density of about 10 mA cm -2, but may not be limited thereto.
  • the overpotential is about -0.01 V to about -0.05 V, about -0.01 V to about -0.04 V, about -0.01 V to about -0.03 V, about -0.01 V to about -0.02 V, about - 0.02 V to about -0.05 V, about -0.02 V to about -0.04 V, about -0.02 V to about -0.03 V, about -0.03 V to about -0.05 V, about -0.03 V to about -0.04 V, or about It may be in the range of -0.04 V to about -0.05 V, but may not be limited thereto.
  • the catalyst for the hydrogen generation reaction may have an overpotential of about -0.01 V to about -0.04 V at a current density of about 10 mA cm -2, but may not
  • the catalyst for the hydrogen evolution reaction may have an AC impedance of about 5 ⁇ to about 15 ⁇ , but may not be limited thereto.
  • the AC impedance may be from about 5 ⁇ to about 15 ⁇ , from about 5 ⁇ to about 14 ⁇ , from about 5 ⁇ to about 12 ⁇ , from about 5 ⁇ to about 10 ⁇ , from about 7 ⁇ to about 15 ⁇ , about 7 ⁇ to about 14 ⁇ , about 7 ⁇ to about 12 ⁇ , about 7 ⁇ to about 10 ⁇ , about 10 ⁇ to about 15 ⁇ , about 10 ⁇ to about 14 ⁇ , or about 10 ⁇ to about 12 ⁇ , This may not be limited.
  • the catalyst for the hydrogen evolution reaction may have an AC impedance of about 7 ⁇ to about 12 ⁇ .
  • a second aspect of the present application provides a device for generating hydrogen energy, including the catalyst for a hydrogen evolution reaction according to the first aspect of the present application.
  • the device for generating hydrogen energy may include a reactor for performing a hydrogen generation reaction using a catalyst for hydrogen generation reaction, but may not be limited thereto.
  • the hydrogen energy generating device may include a fuel cell, but may not be limited thereto.
  • the hydrogen energy generating device may include a connection part between the fuel cell and the reactor for supplying hydrogen generated in the reactor to the fuel cell, but may not be limited thereto. .
  • a filtration means for purifying hydrogen generated in the reactor is provided between the fuel cell and the reactor, in the reactor, and/or It may be further included in the fuel cell, but may not be limited thereto.
  • a third aspect of the present application is, (a) preparing a precursor solution by dissolving a rhodium precursor and a nickel precursor in a mixed solvent containing an alcohol and water having 1 to 5 carbon atoms; (b) electrospin the precursor solution followed by calcination to obtain a single spinel rhodium-nickel oxide nanofiber; and (c) reducing the rhodium-nickel oxide nanofibers to obtain a rhodium-nickel alloy nanofiber, rhodium-provides a method for producing a nickel alloy nanofiber.
  • the rhodium-nickel alloy nanofiber manufacturing method may be performed as shown in FIG. 1 , but may not be limited thereto.
  • each of the rhodium precursor and the nickel precursor may include a halide salt, a nitrate salt, or an acetate salt, for example, chloride, bromide, or It may include iodide, but may not be limited thereto.
  • each of the rhodium precursor and the nickel precursor may be a halide, for example, a chloride, a bromide, or an iodide, but may not be limited thereto.
  • each of the rhodium precursor and the nickel precursor is Rh(NO 3 ) 3 and Ni(NO 3 ) 2 , Rh(OCOCH 3 ) 3 and Ni(OCOCH 3 ) 2 , or RhCl 3 and NiCl It can be two.
  • each of the rhodium precursor and the nickel precursor may include a hydrate, but may not be limited thereto.
  • the rhodium precursor and the nickel precursor may be hydrates, but may not be limited thereto.
  • each of the rhodium precursor and the nickel precursor is Rh(NO 3 ) 3 ⁇ xH 2 O and Ni(NO 3 ) 2 ⁇ yH 2 O, Rh(OCOCH 3 ) 3 ⁇ xH 2 O and Ni(OCOCH 3 ) 2 ⁇ yH 2 O, or RhCl 3 ⁇ xH 2 O and NiCl 2 ⁇ yH 2 O.
  • the molar ratio of the rhodium precursor and the nickel precursor may be about 1: about 0.4 to about 1.1, but may not be limited thereto.
  • a molar ratio of the rhodium precursor and the nickel precursor is about 1: about 0.4 to about 1.1, about 1: about 0.4 to about 1, about 1: about 0.4 to about 0.9, about 1: about 0.4 to about 0.8 , about 1: about 0.4 to about 0.7, about 1: about 0.4 to about 0.6, or about 1: about 0.4 to about 0.5, but may not be limited thereto.
  • the prepared rhodium-nickel oxide may be obtained as a composite oxide rather than a single phase.
  • the molar ratio of the rhodium precursor and the nickel precursor may be about 1: about 0.47 to about 1.07, about 1: about 0.5, or about 2.11: about 1.
  • the alcohol having 1 to 5 carbon atoms is methanol, ethanol, n-propanol, iso-propanol, n-butanol, iso-butanol, sec-butanol, tert-butanol, n-pentanol, iso It may include one or more selected from -pentanol, 3-pentanol, sec-pentanol, and neo-pentanol, but may not be limited thereto.
  • the alcohol having 1 to 5 carbon atoms may be methanol or ethanol.
  • the volume ratio of the alcohol to the water included in the mixed solvent may be about 1: about 0.3 to about 1, but may not be limited thereto.
  • a volume ratio of the alcohol to the water included in the mixed solvent is about 1: about 0.3 to about 1, about 1: about 0.3 to about 0.8, about 1: about 0.3 to about 0.6, about 1: about 0.3 to about 0.3.
  • the volume ratio of the alcohol to the water included in the mixed solvent may be about 1: about 0.4 to about 1, about 1: about 0.4 to about 0.8, or about 1.5: about 0.7.
  • the prepared rhodium-nickel oxide may be obtained as a complex oxide rather than a single phase, but , which may not be limited thereto.
  • the precursor solution may further include polyvinylpyrrolidine, but may not be limited thereto.
  • the rhodium-nickel oxide may include NiRh 2 O 4 .
  • the calcination of (b) may be performed in a temperature range of about 950 °C to about 1,050 °C.
  • the calcination of (b) may be performed in a temperature range of about 950 °C to about 1,050 °C, about 950 °C to about 1,000 °C, or about 1,000 °C to about 1,050 °C.
  • the calcination of (b) may be performed at a temperature of about 1,000 °C or about 1,050 °C.
  • the prepared rhodium-nickel oxide may be obtained as a composite oxide rather than a single phase, but may not be limited thereto. .
  • the calcination of (b) may be performed for about 30 minutes to about 2 hours, but is not limited thereto.
  • the calcination of (b) is from about 30 minutes to about 2 hours, from about 30 minutes to about 1 hour and 30 minutes, from about 30 minutes to about 1 hour, from about 1 hour to about 2 hours, from about 1 hour to about 1 hour. It may be performed for about 1 hour and 30 minutes, or about 1 hour and 30 minutes to about 2 hours, but may not be limited thereto.
  • the calcination of (b) may be performed for about 1 hour.
  • the reduction in (c) may be carried out in a temperature range of about 100 °C to about 300 °C, but may not be limited thereto.
  • the reduction in (c) may be carried out in a temperature range of about 100°C to about 300°C, about 100°C to about 200°C, or about 200°C to about 300°C, but is not limited thereto.
  • the reduction in (c) may be performed for about 1 hour to about 3 hours, but is not limited thereto.
  • the reduction in (c) may be performed for about 1 hour to about 3 hours, about 1 hour to about 2 hours, or about 2 hours to about 3 hours, but may not be limited thereto.
  • the calcination of (b) may be performed for about 2 hours.
  • the calcination of (b) includes being performed in O 2 and He gas atmosphere
  • the reduction of (c) includes being performed in H 2 and Ar gas atmosphere
  • the nickel oxide may be obtained as a composite oxide rather than a single phase, but may not be limited thereto.
  • Nickel chloride hydrate NiCl 2 .6H 2 O, molecular weight: 209.26 g/mol
  • rhodium chloride hydrate RhCl 3 .6H 2 O, molecular weight: 237.69 g/mol
  • polyvinylpyrrolidine PVP, MW ⁇ 1,300,000
  • sodium hydroxide NaOH
  • dibasic sodium phosphate dibasic sodium phosphate
  • Nafion 5 wt% solution
  • Ethyl alcohol was a product of Daejeong (Korea).
  • Perchloric acid (HClO 4 ) was a product of Deoksan (Korea). Commercial Pt/C (20 wt% metal loading on Vulcan XC-72) was purchased from Premetek Company. All solutions used in the experiment were prepared using deionized water (resistance ⁇ 18 M ⁇ cm).
  • Electrospun NiRh 2 O 4 nanofibers were synthesized by electrospinning and post-calcination processes, as shown in FIG. 1 .
  • 35 mg of Ni precursor (NiCl 2 .6H 2 O) and 65 mg of Rh precursor (RhCl 3 .6H 2 O) were dissolved in 2.2 mL of a mixed solvent containing 1.5 mL of ethanol and 0.7 mL of distilled water for 30 min. was sonicated while Then 200 mg of poly(vinylpyrrolidone) was added to the metal precursor solution.
  • the resulting solution was further stabilized under magnetic stirring for 18 hours continuously at room temperature to obtain a fully homogenized solution.
  • the precursor solution thus prepared was placed in a plastic syringe and spun from the needle at a flow rate of 10 ⁇ L ⁇ min ⁇ 1 using an electrospinning system (NanoNC ESR200R2).
  • the distance from the needle tip to the aluminum plate for collecting as the electrospun nanofibers was set to 15 cm, and the applied voltage field was 15 kV, where the temperature was 50 °C and the humidity in the electrospun chamber was less than 20%. It was.
  • the collected spun nanofibers were dried in an oven at 60° C. for 10 minutes immediately after the electrospinning process to remove residual solvent.
  • the electrospun metal precursor/PVP nanofiber was calcined at 1,000° C. for 1 hour under a continuous flow of 15 sccm of O 2 gas and 75 sccm of He gas.
  • the electrospun NiRh 2 O 4 nanofibers were subjected to a reduction process.
  • the electrospun NiRh 2 O 4 nanofibers were calcined at a temperature ranging from 100° C. to 300° C. for 2 hours under a continuous flow of 10 sccm H 2 gas and 90 sccm Ar gas.
  • electrospun pure Rh nanofibers and Ni nanofibers were also synthesized through the same procedure as above.
  • the morphology and composition of the synthesized NiRh 2 O 4 nanofibers and RhNi nanofibers were analyzed using a field-emission scanning electron microscopy (EDS) equipped with an energy dispersive X-ray spectrometer (EDS).
  • EDS energy dispersive X-ray spectrometer
  • FE-SEM JEOL JSM-6700F
  • HRTEM high-resolution transmission electron microscopy
  • X-ray photoelectron spectroscopy X-ray photoelectron spectroscopy
  • XRD high-resolution X-ray diffraction
  • NiRh 2 O 4 nanofibers and RhNi nanofibers were dispersed in deionized water at a concentration of 2 mg ⁇ mL -1.
  • 6 ⁇ L of each well-dispersed sample was loaded onto a glassy carbon (GC) rotating disk and the loaded sample solution was dried in an oven at 50° C. for 15 minutes. The above process was repeated 5 times to load a total of 60 ⁇ L of each catalyst. Then, 10 ⁇ L of 0.05 wt% Nafion (diluted in ethanol) was added dropwise to the GC electrode modified with the synthesized nanofibers and dried in a desiccator for 30 minutes. All electrochemical measurements were performed in a three-electrode cell system.
  • Electrospun NiRh 2 O 4 nanofibers or GC modified with RhNi nanofibers were used as working electrodes.
  • a saturated calomel electrode (SCE) and a coiled Au wire were used as a reference electrode and a counter electrode, respectively.
  • SCE saturated calomel electrode
  • BASi RDE-1 rotor/Epsilon electrochemical analysis
  • N 2 -saturated 1 M NaOH, 1 M PBS and 1 M HClO 4 aqueous solution was performed at an electrode rotation speed of 1600 rpm using an electrochemical analyzer. For all electrochemical measurements, iR drop was corrected.
  • FIG. 2 shows SEM images of nanofibers synthesized through electrospinning and thermal annealing of the solution.
  • FIG. 2(a) is an SEM image of NiRh 2 O 4 nanofibers after thermal annealing process of nanofibers as spun Rh+Ni/PVP, pre-calcined at 1,000° C. for 1 hour under oxidizing conditions.
  • FIG. 2(b) is an SEM image of RhNi nanofibers after thermal annealing of NiRh 2 O 4 under reducing conditions at 200° C. for 2 hours.
  • Figures 2(c) and 2(d) show pure Rh and Ni nanofibers for comparison. Comparing the diameters of all single-phase materials specified in FIG.
  • the diameters of pure Ni nanofibers and Rh nanofibers are 230.14 ( ⁇ 23.80) nm and 167.03 ( ⁇ 25.27) nm, respectively.
  • the diameters of the nanofibers of NiRh 2 O 4 and RhNi@200° C. are 211.91 ( ⁇ 31.35) nm and 175.75 ( ⁇ 27.46) nm, respectively.
  • FIG. 3 shows a low magnification TEM image of NiRh 2 O 4 nanofiber synthesized at 1,000 °C.
  • the estimated interplanar distances of adjacent crystal planes are 0.253 nm, 0.260 nm, 0.301 nm and 0.488 nm, respectively, which are almost identical to the (211), (103), (112) and (101) planes of NiRh 2 O 4 . match
  • the distribution of elements from the EDS region mapping corresponding to Fig. 3(d) [Fig. 3(e) to Fig. 3(g)] shows a uniform atomic distribution of Ni, Rh and O in the NiRh 2 O 4 nanofiber. It was.
  • RhNi @200°C nanofibers derived from the reduction of NiRh 2 O 4 nanofibers also exhibit high crystallinity and uniformity of metal distribution in a single phase manner.
  • Figure 3(h) shows a low-magnification TEM image of the nanofiber of RhNi@200 °C.
  • the HRTEM images and corresponding FFTs demonstrated as Figs. 3(i) and 3(j) show that the distance of adjacent crystal planes is estimated to be about 0.219 nm, which is in close agreement with the (111) lattice of cubic Rh. This means that the prepared RhNi@200°C nanofiber is a single crystal, which indicates atomic embedment through the reduction process of NiRh 2 O 4 .
  • the lattice distance is consistent with the standard (111) and (200) planes of Rh due to the Ni atoms embedded on the Rh atoms in the process of forming the RhNi@200°C alloy nanofibers.
  • 3(k) shows an EDS element mapping image of RhNi nanofibers, and it can be seen that Rh and Ni atoms are uniformly distributed [ FIGS. 3(l) and 3(m)].
  • NiRh 2 O 4 and RhNi@200° C. nanofibers can be further described by XRD (X-ray diffraction) of FIG. 4 to elucidate the phase and crystal structure.
  • XRD X-ray diffraction
  • the observed diffraction peak corresponds to the reference NiRh 2 O 4 (JCPDS 73-1040), indicating a distinct peak-matching located between 10° and 80°.
  • JCPDS 73-1040 reference NiRh 2 O 4
  • NiRh 2 O 4 synthesized based on previous studies is in good agreement with the XRD results of Dulac, J. Since the diffraction peak of RhNi@200°C generated through the reduction process of NiRh 2 O 4 nanofibers is found between pure Rh and Ni metal, Ni with a smaller atomic radius than Rh embedded in the Rh cubic lattice deforms the tensile lattice. It represents the formation of alloys causing tensile lattice strain. This result is consistent with the results of HRTEM and FFT, as shown in FIG. 3 .
  • FIG. 5 The surface element composition of the nanomaterial and its valence states explained by the results of X-ray photoelectron spectroscopy are shown in FIG. 5 .
  • the low-resolution irradiation spectrum of NiRh 2 O 4 and RhNi@200° C. nanofibers on a Si substrate indicates the presence of Rh and Ni elements in a specific binding energy region.
  • Fig. 5(c) shows the Rh 3d spectrum of NiRh 2 O 4 and RhNi@200° C. nanofibers compared to the 3d peak of metallic pure Rh. The peaks located at 307.7 eV and 312.5 eV correspond to Rh 0 3d 5/2 and Rh 0 3d 3/2 of metallic Rh, respectively.
  • the binding energies of 3d 5/2 and 3d 3/2 in NiRh 2 O 4 are more positive, indicating that Rh has more positive charge in NiRh 2 O 4 . indicates.
  • the 3d 5/2 and 3d 3/2 peaks in NiRh 2 O 4 are centered at 308.4 eV and 313.3 eV, but at the standard values of Rh 2 O 3 (313.2 eV for 3d 3/2 and 308.5 eV for 3d 5/2 ). very close.
  • Rh of the RhNi@200°C nanofibers show 307.4 eV and 312.1 eV, indicating that Rh of the RhNi@200°C nanofiber has less positive charge compared to the 3d peak of metallic Rh.
  • Rh of the RhNi@200°C nanofiber may attract electrons more strongly than Ni, resulting in a negative binding energy than the metal Rh.
  • Figure 5(d) shows the 2p spectrum of the NiRh 2 O 4 and RhNi@200° C. nanofibers compared to the metallic Ni spectrum.
  • the peaks located at 851.8 eV and 869.2 eV correspond to Ni 0 2p 3/2 and Ni 0 2p 1/2 of metallic Ni, respectively.
  • the Ni metal has a complex shape such as a satellite shape corresponding to 2p 3/2 and 2p 1/2 satellites, respectively.
  • the binding energies of 2p 3/2 and 2p 1/2 in NiRh 2 O 4 are more positive, indicating that Ni atoms in NiRh 2 O 4 have more positive charge.
  • Ni 2p spectrum of Ni oxide which has an oxidation state of +2 rather than the valence state of the metal
  • the Ni 2p binding energy of NiRh 2 O 4 are multiple splits of Ni 2p 3/2 and 2p 1/2 . (multiplet-splitting) corresponding to NiO located at binding energies of about 855 eV and 870 eV.
  • the peaks located at 862 eV and 880 eV in NiRh 2 O 4 are similar to the satellite spectrum of Ni 2p in NiO.
  • the Ni atom of the NiRh 2 O 4 nanofiber has an oxidation state of +2 than the metallic state or other low oxidation state.
  • the binding energies of the 2p peak of RhNi@200°C nanofibers are 852.8 eV and 870.2 eV, indicating that Ni at RhNi@200°C has a more positive charge compared to the 2p peak of metallic Ni.
  • the two peaks were slightly shifted towards the higher binding energy in the case of RhNi@200°C, which is related to the difference in electronegativity with adjacent Rh atoms.
  • Ni atoms are less electronegative than Rh atoms. Therefore, it is estimated that the transfer of the binding energy may cause a positive binding energy than metallic Ni by strongly attracting the Ni valence electrons at RhNi@200°C to the Rh atom.
  • 6(a) and Fig. 6(d)] neutral [Fig. 6(b) and Fig. 6(e)] and acidic [Fig. 6(c) and Fig. 6(f)) )] were performed sequentially.
  • 6(a) and 6(d) show LSV curves and Tafel plots of nanofibers synthesized in 1 M NaOH(aq) in basic solution. The best HER activity with lower onset potential and greater current density than Pt/C is obtained as well as the highest HER activity reported so far for RhNi@200°C nanofibers. The improved efficiency for hydrogen production obtained by RhNi@200°C was also shown from the Tafel plot.
  • RhNi@200°C shows the best HER catalyst performance compared to Pt/C.
  • the curves of Figures 6(b) and 6(e) in neutral solution were LSV and Tafel plots in 1M PBS solution. RhNi@200°C has slightly lower overpotential than Pt/C, but the current increase according to potential is greater at RhNi@200°C.
  • the Tafel slope of the RhNi@200°C nanofiber shows an increase rate almost equal to that of Pt/C, where the increase in HER rate as the overpotential increases is almost the same on both sides.
  • RhNi@200°C nanofiber exhibits an overpotential as low as Pt/C but a sharp current density gradient. Therefore, when the potential is non-negative than -40 mV, the cathodic current of RhNi@200 °C nanofibers exceeds that of Pt/C, but the two curves show similar current densities after -40 mV. This similar current density versus potential is also shown in the Tafel slope comparison. The improvement of the HER activity of the electrocatalyst to achieve better activity than Pt/C with the highest HER activity reported so far was demonstrated as shown in FIG. 6 .
  • RhNi@200°C nanofibers as hydrogen evolution catalysts (HECs) exhibited excellent electrochemical activity in all-pH media, where HECs were not commonly reported in all-pH media.
  • HECs hydrogen evolution catalysts
  • RhNi@200° C. has the smallest Faraday impedance among nanofibers compared in 1.0 M NaOH (aq), 1.0 M PBS (aq) and 1.0 M HClO 4 (aq) ( Zf) is shown;
  • the Zf values of RhNi@200° C., Rh pure metal nanofibers, Ni pure metal nanofibers, and NiRh 2 O 4 nanofibers in 1.0 M NaOH (aq) were 11.36 ⁇ , 29.82 ⁇ , 59.21 ⁇ , and 96.84 ⁇ , respectively.
  • the Zf values of RhNi@200° C., Rh pure metal nanofibers, Ni pure metal nanofibers, and NiRh 2 O 4 nanofibers in 1.0 M PBS (aq) were 7.34 ⁇ , 27.50 ⁇ , 199.90 ⁇ and 51.72 ⁇ , respectively.
  • the Zf values of RhNi@200° C., Rh pure metal nanofibers, Ni pure metal nanofibers, and NiRh 2 O 4 nanofibers in 1.0 M HClO 4 (aq) were 7.34 ⁇ , 27.21 ⁇ , 52.24 ⁇ , and 87.92 ⁇ , respectively.
  • RhNi@200°C exhibits the smallest Faraday impedance at different pH solutions, as identified by facile HER kinetics among the materials tested to corroborate the LSV measurement.
  • Catalyst stability is another important criterion for a good HER electrocatalyst. Additional experiments providing further analysis of the stability of the synthetic material were performed in 1 M NaOH, 1 M PBS and 1 M HClO 4 for repeated potential cycling at a specific potential generating 10 mA ⁇ cm ⁇ 2 . For more accurate comparison, potentials with a current of 10 mA ⁇ cm -2 were compared every 100 scans. As shown in FIGS. 8(a) to 8(f) , the potentials generating 10 mA ⁇ cm ⁇ 2 during 1,000 repeated scans in all media hardly changed.
  • the average potential in 1 M HClO 4 (aq) during 1,000 repeated scans was -0.015 V ( ⁇ 0.002), and the change in potential was measured from -0.011 V in the first scan to -0.017 V in 1,000 scans, repeated For 1,000 scans of 1 M NaOH (aq), the average potential was -0.011 V ( ⁇ 0.004), and the potential change was measured from -0.007 V in the first scan to -0.018 V in the 1,000th scan.
  • the average potential in 1 M PBS (aq) during 1,000 repeated scans was -0.019 V ( ⁇ 0.002), and the change in potential was measured from -0.016 V in the first scan to -0.024 V in the 1,000th scan.
  • RhNi@200°C not only has comparable catalytic activity to Pt/C at low overpotential and high current density, but is also stable for 1,000 repeated cycles at a real working potential generating 10 mA cm ⁇ 2 . do. These results clearly indicate that RhNi@200°C is an electrocatalyst with very good activity in a wide pH range. Significantly, RhNi@200° C. shows good stability under all-pH aqueous solutions.
  • NiRh 2 O 4 is a composite oxide rather than a single phase
  • the material before reduction should be a single-phase NiRh 2 O 4 .
  • the material before reduction was in a mixed state of complex oxides (NiO and Rh 2 O 3 ) rather than a single phase
  • the material obtained after reduction was also in a composite state rather than a single phase.
  • the reduction temperature of 200 ° C was sufficient to synthesize the RhNi binary alloy nanofibers
  • the material reduced from the composite oxide showed a NiO peak at 200 ° C.
  • the material in the oxide state was not produced.
  • the XRD data according to FIG. 9 proves that NiRh 2 O 4 of a single phase is required as a material before reduction in order to synthesize a RhNi binary alloy. Accordingly, conditions for synthesizing single-phase NiRh 2 O 4 were examined.
  • RhNi @ 200 °C alloy nanofiber was synthesized from NiRh 2 O 4 spinel single phase as a reduced form of the alloy RhNi H 2 under reducing conditions NiRh 2 O 4.
  • the catalytic activity was performed in NaOH, PBS and HClO 4 aqueous solution.
  • RhNi@200°C alloy nanofibers have low overpotentials at 10 mA cm ⁇ 2 and small Tafel gradients in all-pH solutions that outperform Pt/C, pure Rh metal and other previously reported other Rh or Ni-based catalysts.
  • RhNi@200°C alloy nanofibers show high stability change during 1,000 repeated scans in all media.
  • alloys superior to pure metals in HER generally have improved activity due to several factors.

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Abstract

La présente invention concerne un catalyseur de réaction d'évolution d'hydrogène comprenant des nanofibres d'alliage rhodium-nickel, un générateur d'énergie hydrogène le comprenant, et un procédé de fabrication des nanofibres d'alliage rhodium-nickel.
PCT/KR2020/014791 2019-12-17 2020-10-28 Catalyseur de réaction d'évolution d'hydrogène comprenant des nanofibres d'alliage rhodium-nickel, et procédé de fabrication de nanofibres d'alliage rhodium-nickel WO2021125543A1 (fr)

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