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EP3380651B1 - Électrode sous forme de fibre creuse métallique - Google Patents

Électrode sous forme de fibre creuse métallique Download PDF

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Publication number
EP3380651B1
EP3380651B1 EP16820029.3A EP16820029A EP3380651B1 EP 3380651 B1 EP3380651 B1 EP 3380651B1 EP 16820029 A EP16820029 A EP 16820029A EP 3380651 B1 EP3380651 B1 EP 3380651B1
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Prior art keywords
hollow fiber
fibers
copper
hollow
metal
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EP3380651A1 (fr
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Recep KAS
Patrick DE WIT
Nieck Edwin Benes
Guido Mul
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Twente Universiteit
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Twente Universiteit
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    • 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
    • C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
    • C25B11/02—Electrodes; Manufacture thereof not otherwise provided for characterised by shape or form
    • 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
    • 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
    • C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
    • C25B11/02—Electrodes; Manufacture thereof not otherwise provided for characterised by shape or form
    • C25B11/03—Electrodes; Manufacture thereof not otherwise provided for characterised by shape or form perforated or foraminous
    • C25B11/031—Porous electrodes
    • 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
    • C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
    • C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
    • C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
    • C25B11/055—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the substrate or carrier material
    • C25B11/057—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the substrate or carrier material consisting of a single element or compound
    • 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
    • C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
    • C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
    • C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
    • C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
    • C25B11/075—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of a single catalytic element or catalytic compound
    • 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
    • C25B3/00—Electrolytic production of organic compounds
    • C25B3/20—Processes
    • C25B3/25—Reduction

Definitions

  • the invention is directed to a metal hollow fiber electrode, to a method of electrolyzing carbon dioxide in an aqueous electrochemical cell, to a method of converting carbon dioxide, to a method of preparing a metal hollow fiber, to a use of a metal hollow fiber electrode.
  • Copper electrodes are well known for producing hydrocarbons from CO 2 with variable onset potentials ( ⁇ 0.5-0.7 V) depending on the preparation method. Generally, high potentials ( ⁇ 0.8-1 V) are necessary to obtain reasonable faradaic efficiency (FE). Although less expensive and much more abundant than other CO evolving catalysts such as e.g. silver and gold, poor activity, selectivity and stability towards CO and formic acid have been reported for polycrystalline copper. Recently, Li et al. reported production of CO and formic acid with reasonable faradaic efficiency at low overpotentials on copper nanoparticles, when formed by electrochemical reduction of cuprous oxides [ Li et al., J. Am. Chem. Soc. 2012, 134, 7231-7234 ].
  • Inorganic hollow fibers are of potential significance for solid oxide fuel cells due to their high surface area to volume ratio, higher power outputs and lower fabrication costs, but utilization in room temperature solution based electrochemistry is quite rare.
  • nickel and carbon hollow fibers with dual functionality, where they served as both membrane for effluent purification and as cathode for proton and oxygen reductions, respectively.
  • microtubular gas diffusion electrodes made of carbon nanotubes were proposed for tubular electrochemical reactor design [ Gendel et al., Electrochem. Commun. 2014, 46, 44-47 ].
  • An objective of the invention is to overcome one or more disadvantages seen in the prior art.
  • a further objective of the invention is to provide an electrode that allows low pressure and room temperature electrolysis of CO 2 .
  • the invention is directed to a metal hollow fiber electrode, comprising aggregated cooper particles forming an interconnected three-dimensional porous structure, wherein said metal comprises copper.
  • metal hollow fiber electrodes can be a potential candidate for low pressure and room temperature electrolysis of CO 2 , due to their excellent mass transport capabilities when used as gas diffuser and cathode. Not only the hydrogen evolution reaction is suppressed on these electrodes to levels not reached previously on copper surfaces, but also the overall CO 2 reduction current density is unprecedentedly high at low potentials.
  • the metal comprises copper and other metals may optionally be present. More preferably, the metal is copper.
  • the metal hollow fibers can typically have an inner diameter of 0.1-10 mm, such as 0.5-5 mm, or 0.7-3 mm.
  • the outer diameter of the metal hollow fibers can be 0.1-10 mm, such as 0.5-5 mm, or 0.7-3 mm.
  • the fibers preferably comprise, or are composed of, sintered copper particles.
  • Solid state sintering is the process of taking metal in the form of a powder and placing it into a mold or die. Once compacted into the mold the material is placed under a high heat for a long period of time. Under heat, bonding takes place between the porous aggregate particles and once cooled the powder has bonded to form a solid piece.
  • the copper particles in the metal hollow fiber electrode preferably have an average particle diameter of 0.1-10 ⁇ m, such as 0.3-5 ⁇ m, or 0.5-3 ⁇ m.
  • a porous outer layer of the hollow fiber is more dense than a porous inner layer of the hollow fiber, said outer layer preferably having a thickness in the range of 5-20 ⁇ m, such as 12-18 ⁇ m, or 10-15 ⁇ m.
  • the preparation of the metal hollow fibers i.e. nickel and stainless steel has been described in the literature previously [ Meng et al., J. Alloy Compd. 2009, 470, 461-464 ; Luiten-Olieman et al., Scripta Mater. 2011, 65, 25-28 ].
  • the preparation of Cu hollow fiber has not been reported to the best of our knowledge.
  • the inventors adapted the method and prepared Cu hollow fibers by spinning a mixture containing copper particles, polymer and solvent. The mixture is suitably pressed through a spinneret into a coagulation bath. In this bath, non-solvent induced phase separation arrests the copper particles in the polymer matrix. By adding a bore-liquid during spinning, a hollow fiber is obtained.
  • Cu hollow fibers can have outer and inner diameters ranging from 1.55 ⁇ 0.1 mm to 1.3 ⁇ 0.05 mm respectively ( figure 1e ).
  • CO 2 was pushed from the inside out of the fiber, creating an overpressure around 1.70 ⁇ 0.1 bars due to the resistance of the porous structure. Gas bubbles emerging out of the fiber can be clearly seen in figure If. The pressure is considered to spread out the finger-like holes without resistance and to drop across the porous outer layer to 1.05 bar.
  • electrochemical reduction likely takes place both at the interface of CO 2 (g) and water (1) in contact with copper (s), as well as near the electrode surface with dissolved CO 2 .
  • the faradaic efficiency of the major products was measured by varying the applied potential between -0.15 V and -0.55 V vs. RHE ( figure 2b ).
  • the onset of CO formation is located at -0.15 V vs. RHE, implying an overpotential of just ⁇ 40 mV above the equilibrium potential (-0.11 V vs. RHE).
  • the total faradaic efficiency of the CO 2 reduction products adds up to ⁇ 85 % at potentials between -0.3 V and -0.5 V vs. RHE.
  • a peak faradaic efficiency of ⁇ 72 % was obtained for CO at a potential of -0.4 V vs.
  • the first step involves an electron transfer to adsorbed CO 2 which is coupled to a proton transfer.
  • COOH intermediate accepts an electron and proton to form CO and water.
  • a slope around 116 mVdec -1 was recorded for copper different electrodes that suggests a mechanism in which initial electron transfer to CO 2 is rate determining.
  • the lower slope of 93 mVdec -1 associated with the lower potential region is most likely due to non-uniform potential or current distribution within the solid porous matrix of the hollow fiber.
  • X-ray photoelectron spectroscopy (XPS) analysis of the precursor copper powder and Cu hollow fibers before the and after electrolysis experiments indicated that there is no detectable amount (> % 0.1) of transition metal impurity at the surface of the catalyst ( figure 12 ).
  • the major impurity within the hollow fiber is carbon which is also present in the precursor copper powder.
  • XPS spectra of the fibers indicated the surface is composed of mainly with Cu 0 and Cu 2 O, the latter associated with the exposure of the sample to air ( figure 13 ). More importantly, the absence of shift in binding energy of Cu2p peaks before and after preparation and electrolysis suggests the absence of any alloy or carbide formation upon annealing or electrolysis.
  • Figures 3a and 3b show the effect of the CO 2 flow rate on overall current density and faradaic efficiency of CO at an applied voltage of -0.4 V vs. RHE, respectively.
  • the current density undoubtedly is proportional to the CO 2 flow rate above -0.35 V vs. RHE, until a certain flow rate was reached.
  • the change in faradaic efficiency of CO is consistent with the increase in current density.
  • a maximum faradaic efficiency of 75 % was recorded for CO at a potential of -0.4 V vs. RHE at optimized flow rate which is almost twice of what has been recently reported for copper nanoparticles at the same potential.
  • the experiments as a function of flow rate indicate that the faradaic efficiency of CO strictly depends on supply of CO 2 to the electrode surface.
  • the high faradaic efficiencies observed in this study is a result of improved mass transfer of CO 2 integrated with the defect rich, active and porous copper electrode.
  • the steady behavior above the flow rate of 30 ml min -1 implies all the active sites are involved in converting CO 2 to CO, and the catalyst has reached its intrinsic limit.
  • the CO 2 reduction rate in aqueous conditions was shown to be proportional to the CO 2 pressure on different metal electrodes, suggesting high degrees of coverage were not achieved even at pressures as high as 25 atm.
  • the intermediate CO was considered to have a high degree of coverage during electrochemical CO 2 reduction on copper electrodes, supported by spectroscopic studies.
  • the high current densities achieved on Cu hollow fibers is attributed to better removal of CO from the surface, induced by a very high local concentration of CO 2 near the electrode. Besides an improved performance, this also enables the evaluation of the intrinsic activity of the electrocatalyst especially when a competing reaction, i.e. hydrogen evolution, simultaneously takes place.
  • Cu hollow fibers While outcompeting the currently best performing copper based electrodes, Cu hollow fibers also show comparable activities at low potentials (-0.2 V to -0.6 V vs. RHE) to that of noble metal catalysts evaluated in aqueous solutions (Au nanoparticles, nanoporous Ag). It should be recalled that noble metal electrodes benefit from a high overpotential for hydrogen evolution, while Cu hollow fibers perform so well on the basis of the improved mass transfer of CO 2 .
  • the thickness of the porous catalyst layer used in gas diffusion electrodes is typically in the range from 5-20 ⁇ m, similarly for copper hollow fibers, the electrode thickness that participates into the electrolysis is around 15-20 ⁇ m estimated from nickel electrodeposition and subsequent energy dispersive X-ray analysis ( figure 10 ). This thickness is also comparable to oxide films used to prepare rough electrodes or electrodeposited 3-D porous structures employed as electrodes.
  • the geometrical current density of the fibers are calculated by normalizing the current to the outer surface area of the cylindrical hollow fibers. In addition, it is a common practice to use the projected area of the 3-D electrode, or so called apparent area, in conventional gas diffusion electrodes to report current densities.
  • the mature dry-wet spinning process allows mass production of organic hollow fibers that are already commercially available.
  • Microtubular geometry has been deployed and investigated in solid oxide fuel cells for decades which could allow the adaptation of technologies developed such as stack design, sealing, current collection etc..
  • Metal hollow fibers might provide cost effective and compact diffusion media and/or catalyst layer for gas diffusion electrodes which might also eliminate resistance associated with catalyst support interface.
  • the thickness of the active catalyst layer can be tuned by changing 3-D geometry, support material, porosity and/or precursor particle size, to further optimize the production rate.
  • the invention is directed to a method of electrolyzing carbon dioxide in an aqueous electrochemical cell comprising an anode and a cathode, wherein the cathode comprises one or more metal hollow fiber electrodes according to the invention, said method comprising
  • the method of the invention is performed in an aqueous environment.
  • the method can suitably be performed at a temperature in the range of 5-80 °C, such as in the range of 10-30 °C, more preferably in the range of 15-25 °C.
  • the invention is directed to a method of converting carbon dioxide into one or more selected from the group consisting of carbon monoxide, formic acid, a formate, methanol, acetaldehyde, methane, ethylene and ethane, comprising electrolyzing CO 2 by a method according to the invention of electrolyzing carbon dioxide in an aqueous electrochemical cell comprising an anode and a cathode as described herein.
  • the carbon dioxide is converted into carbon monoxide.
  • the invention is directed to a method of preparing a metal hollow fiber electrode according to the invention, comprising:
  • the thermal treatment in this method preferably comprises subjecting the hollow fibers to a temperature in the range of 500-800 °C, such as in the range of 550-700 °C. This thermal treatment is preferably performed for a period of 1-6 hours, such as a period of 2-5 hours.
  • the hydrogenation preferably comprises subjecting the hollow copper oxide fibers to a temperature in the range of 200-400 °C, such as in the range of 250-350 °C. This hydrogenation is preferably performed for a period of 30-120 minutes, such as 45-90 minutes.
  • the hydrogenation comprises subjecting the hollow copper oxide fibers to a flow of hydrogen in the concentration range of 0.1-100 vol.%, such as 5 vol.% in a balance gas.
  • the invention is directed to the use of a metal hollow fiber electrode according to the invention as cathode and/or gas diffuser.
  • Spinning was carried out at room temperature (21 ⁇ 3 °C) using a stainless steel vessel, that was pressurized to 1 bar using nitrogen. The mixture was pressed through a spinneret (inner and outer diameters of 0.8 mm and 2.0 mm, respectively) into a coagulation bath containing tap water. Deionized water was pumped through the bore of the spinneret with a speed of 30 ml min -1 and the air gap was set to 1 cm.
  • the fibers were kept in the coagulation bath for 1 day to remove traces of NMP, followed by drying for 1 day.
  • the green copper hollow fibers were thermally treated at 600 °C for 3 hours (heating rate and cooling rates: 1 °C min -1 ) in air to remove the PEI and subsequent sintering of the copper particles.
  • the oxidized hollow fibers were reduced by hydrogenation at 280 °C for 1 hour (H 2 in Argon: 4 %, heating rate and cooling rate: 100 °C/min).
  • X-ray diffraction patterns were collected by using a Bruker D2 Phaser x-ray diffractometer, equipped with a Cu-K ⁇ radiation source and operated at 30 kV and 10 mA ( figure 5 ).
  • X-ray photoelectron spectroscopy (XPS) spectrum was collected by using Quantera SXM (Scanning XPS microprobe) spectrometer equipped with Al K ⁇ (1486.6 eV) X-ray source. The source was operated with a 25 W emission power, beam size of 200 ⁇ m and pass energy of 224 eV. The resolution of the spectrometer was 0.1eV and 0.2 eV for high resolution element scan and survey spectra, respectively.
  • Electrochemical CO 2 reduction activity of Cu HF's was measured by using three electrode assembly in a glass cell at room temperature and pressures. A Princeton Applied Research versaSTAT 3 potentiostat was used to control the potentials. The counter electrode, Pt mesh, was separated by using a Nafion 112 membrane (Sigma Aldrich). An Ag/AgCl (3 M NaCl BASI) reference electrode was placed near the working electrode by using a Luggin capillary and all the potentials were converted to RHE scale afterwards. IR drops were measured before the electrolysis and compensated manually after the experiments.
  • thermal conductivity detector TCD
  • flame ionization detector FID
  • TCD thermal conductivity detector
  • FID flame ionization detector
  • the time needed to reach steady state concentration was approximately 10 minutes so all the reaction times were kept at least 20 minutes.
  • a control experiment was conducted at -0.5 V vs. RHE under Argon atmosphere. No CO was detected that might associated with the organic residues remaining from polymers that is used during preparation of the hollow fibers.
  • Liquid products formed during the electrolysis were analyzed by using High Performance Liquid Chromatography (HPLC) (Prominence HPLC, Shimadzu; Aminex HPX 87-H column, Biorad).
  • HPLC High Performance Liquid Chromatography
  • Nickel deposition was performed from solutions of nickel nitrate (50 mM Ni(NO 3 ) 2 , 5 mA cm -2 for 900 s) while purging Ar at 20 ml min -1 .
  • the SEM images in figure 10 show that the nickel deposition takes place mostly on the outer surface.
  • Energy dispersive X-ray analysis (EDX) showed that the penetration depth of Nickel through the fiber is around 15-20 ⁇ m which indicates the thickness of the electrode utilized during the CO 2 reduction.
  • the noisy character of the line scan is due to porous nature of the Cu hollow fiber.
  • the current values obtained are normalized by the external geometrical surface area of the cylindrical Cu hollow fibers.
  • the current density is calculated by using the geometrical area of the electrode.
  • the thickness of the electrode utilized during CO 2 reduction in this study is comparable to 3-D porous and nanostructured surfaces.
  • gas diffusion electrodes it is common to use the projected area of the 3-D electrode.
  • the electrochemical active surface area is important to interpret the catalytic activity of the fibers, whereas the geometrical current density is important for the practical applications.
  • X-ray photoelectron spectroscopy was collected by using Quantera SXM (Scanning XPS microprobe) spectrometer equipped with Al K ⁇ (1486.6 eV) X-ray source. The source was operated with a 25 W emission power, beam size of 200 ⁇ m and pass energy of 224 eV. The resolution of the spectrometer was 0.1 eV and 0.2 eV for high resolution element scan and survey spectra, respectively. High resolution elemental scans are performed for Cu, C, O, Al, Ni, Fe, Pb, Cd, Hg. The minimal detectable amount changes with the sensitivity factors for the elements. As a rule of thumb: lighter elements have smaller sensitivity factors and are less good detectable than heavy elements.
  • the calculated amounts for the detected elements are given in table 3.
  • the elemental scan Cu 2p XPS spectrum indicated the presence of Cu 0 and/or Cu 1+ , but the peaks associated with Cu 2+ in all the spectra were absent.
  • Cu 0 and Cu 1+ ratio can be roughly estimated by using Cu LMM peaks ( figure 14 ).
  • There are minor impurities at the surface of the Cu hollow fiber before electrolysis which are most like associated with the polymers used in spinning process. These impurities are removed upon electrolysis.
  • Table 3 The atomic concentrations of the elements calculated from the intensities of the peaks present in XPS spectra Sample C N O Na S Cl Ca Cu Cu 0 /C + From Cu LMM fit Cu Powder 9.39 - 43.87 - - - - 46.74 21/79 Cu Fiber (before) 28.82 0.65 44.76 1.15 1.30 0.28 0.37 22.67 52/48 Cu Fiber (after) 7.53 - 42.40 - - - - 50.06 73/27

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  • Organic Chemistry (AREA)
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Claims (15)

  1. Electrode sous forme de fibre creuse métallique, comprenant des particules de cuivre agrégées formant une structure poreuse tridimensionnelle interconnectée, dans laquelle ledit métal comprend ou est du cuivre.
  2. Electrode sous forme de fibre creuse métallique selon la revendication 1, dans laquelle lesdites fibres ont un diamètre intérieur de 0,1-10 mm, de préférence 0,5-5 mm, plus préférentiellement 0,7-3 mm, et/ou ont un diamètre extérieur de 0,1-10 mm, de préférence 0,5 à 5 mm, et mieux encore de 0,7 à 3 mm.
  3. Electrode sous forme de fibre creuse métallique selon la revendication 1 ou 2, dans laquelle ladite fibre comprend ou est composée de particules de cuivre frittées.
  4. Electrode sous forme de fibre creuse métallique selon l'une quelconque des revendications 1 à 3, dans laquelle lesdites particules de cuivre ont un diamètre de particules moyen de 0,1 à 10 µm, de préférence de 0,3 à 5 µm, de manière davantage préférée de 0,5 à 3 µm.
  5. Electrode sous forme de fibre creuse métallique selon l'une quelconque des revendications 1 à 4, dans laquelle une couche externe poreuse de la fibre creuse est plus dense qu'une couche interne poreuse de la fibre creuse.
  6. Electrode sous forme de fibre creuse métallique selon la revendication 5, dans laquelle ladite couche externe a une épaisseur dans la plage de 5 à 20 µm, de préférence de 12 à 18 µm, plus préférablement de 10 à 15 µm.
  7. Procédé d'électrolyse de dioxyde de carbone dans une cellule électrochimique aqueuse comprenant une anode et une cathode, dans lequel la cathode comprend une ou plusieurs électrodes formées de fibres creuses métalliques selon l'une quelconque des revendications 1 à 6, ledit procédé comprenant
    - l'application d'un potentiel entre ladite anode et la cathode, et
    - la purge du CO2 ou d'un mélange gazeux comprenant du CO2 à travers la paroi de l'électrode formé de fibres creuses métalliques,
    ledit procédé étant de préférence effectué dans un environnement aqueux.
  8. Procédé selon la revendication 7, dans lequel ledit procédé est effectué à une température dans la plage de 5 à 80°C, de préférence de 10 à 30°C, plus préférablement de 15 à 25°C.
  9. Procédé de conversion du dioxyde de carbone en un ou plusieurs composés choisis dans le groupe constitué par le monoxyde de carbone, l'acide formique, un formiate, le méthanol, l'acétaldéhyde, le méthane, l'éthylène et l'éthane, comprenant l'électrolyse du CO2 par un procédé selon la revendication 7 ou 8,
    dans lequel de préférence, le dioxyde de carbone est converti en monoxyde de carbone.
  10. Procédé de préparation d'une électrode métallique à fibre creuse selon l'une quelconque des revendications 1 à 6, comprenant
    - le filage d'un mélange comprenant des particules de cuivre, un polymère et un solvant avec un liquide d'alésage pour obtenir des fibres creuses;
    - l'étape consistant à soumettre les fibres creuses à un traitement thermique tel que les particules de cuivre soient frittées ensemble, donnant ainsi des fibres creuses d'oxyde de cuivre;
    - l'hydrogénation des fibres creuses d'oxyde de cuivre,
    dans lequel ledit traitement thermique comprend de préférence la soumission des fibres creuses à une température de 500 à 800°C, plus préférablement à une température de 550 à 700°C.
  11. Procédé selon la revendication 10, dans lequel les fibres creuses sont soumises audit traitement thermique pendant une période de 1 à 6 heures, de préférence pendant une période de 2 à 5 heures.
  12. Procédé selon la revendication 10 ou 11, dans lequel ladite hydrogénation comprend la soumission des fibres creuses d'oxyde de cuivre à une température de 200 à 400°C, de préférence à une température de 250 à 350°C.
  13. Procédé selon l'une quelconque des revendications 10 à 12, dans lequel les fibres creuses d'oxyde de cuivre sont hydrogénées pendant une période de 30 à 120 minutes, de préférence de 45 à 90 minutes.
  14. Procédé selon l'une quelconque des revendications 10-13, dans lequel les fibres creuses d'oxyde de cuivre sont hydrogénées dans un flux d'hydrogène dans la plage de concentration de 0 à 100 vol.%, de préférence une concentration de 5 vol.% dans un gaz de dilution.
  15. Utilisation d'une électrode à fibres creuses métalliques selon l'une quelconque des revendications 1 à 6 comme cathode et/ou diffuseur de gaz.
EP16820029.3A 2015-11-24 2016-11-24 Électrode sous forme de fibre creuse métallique Active EP3380651B1 (fr)

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JP6779849B2 (ja) * 2017-09-19 2020-11-04 株式会社東芝 二酸化炭素の還元触媒体とその製造方法、還元電極、及び還元反応装置
KR102140710B1 (ko) * 2018-06-22 2020-08-03 한국과학기술원 이산화탄소 전환용 고압 반응조 및 이의 운영 방법
CN114395777A (zh) * 2022-01-17 2022-04-26 中国科学院上海高等研究院 一种金属自支撑电极、制备方法和应用
CN114959761B (zh) * 2022-05-05 2023-11-03 中国科学院上海高等研究院 一种银中空纤维电极的制备方法及应用

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US20150136613A1 (en) * 2013-02-12 2015-05-21 The Board Of Trustees Of The Leland Stanford Junior University Catalysts for low temperature electrolytic co reduction
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