EP4209619A1 - Procédé et utilisation d'un matériau d'électrocatalyseur à base de cuivre dans un électrolyte sursaturé - Google Patents

Procédé et utilisation d'un matériau d'électrocatalyseur à base de cuivre dans un électrolyte sursaturé Download PDF

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EP4209619A1
EP4209619A1 EP22305020.4A EP22305020A EP4209619A1 EP 4209619 A1 EP4209619 A1 EP 4209619A1 EP 22305020 A EP22305020 A EP 22305020A EP 4209619 A1 EP4209619 A1 EP 4209619A1
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mol
electrolyte
electrodeposition
gas
conductive support
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EP22305020.4A
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German (de)
English (en)
Inventor
Damien Voiry
Kun QI
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Centre National de la Recherche Scientifique CNRS
Universite de Montpellier I
Ecole Nationale Superieure de Chimie de Montpellier ENSCM
Universite de Montpellier
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Centre National de la Recherche Scientifique CNRS
Universite de Montpellier I
Ecole Nationale Superieure de Chimie de Montpellier ENSCM
Universite de Montpellier
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Priority to EP22305020.4A priority Critical patent/EP4209619A1/fr
Publication of EP4209619A1 publication Critical patent/EP4209619A1/fr
Withdrawn legal-status Critical Current

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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
    • C25B3/00—Electrolytic production of organic compounds
    • C25B3/01—Products
    • C25B3/07—Oxygen containing compounds
    • 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
    • C25B11/032—Gas diffusion 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
    • C25B11/052—Electrodes comprising one or more electrocatalytic coatings on a substrate
    • 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
    • C25B11/065—Carbon
    • 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
    • C25B11/089—Alloys
    • 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
    • C25B3/26—Reduction of carbon dioxide
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D3/00—Electroplating: Baths therefor
    • C25D3/02—Electroplating: Baths therefor from solutions
    • C25D3/56—Electroplating: Baths therefor from solutions of alloys
    • C25D3/58—Electroplating: Baths therefor from solutions of alloys containing more than 50% by weight of copper
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D3/00—Electroplating: Baths therefor
    • C25D3/02—Electroplating: Baths therefor from solutions
    • C25D3/56—Electroplating: Baths therefor from solutions of alloys
    • C25D3/64—Electroplating: Baths therefor from solutions of alloys containing more than 50% by weight of silver
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/003—Electroplating using gases, e.g. pressure influence
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/60—Electroplating characterised by the structure or texture of the layers
    • C25D5/605—Surface topography of the layers, e.g. rough, dendritic or nodular layers
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/60—Electroplating characterised by the structure or texture of the layers
    • C25D5/615—Microstructure of the layers, e.g. mixed structure
    • C25D5/617—Crystalline layers

Definitions

  • the present invention belongs to the field of catalytic chemistry, and more specifically to catalyzed reduction chemical reactions, preferably the reduction of CO 2 into small molecules.
  • the present invention relates to a new copper based electrocatalyst material and its method of preparation comprising a step of in-situ electrodeposition or co-electrodeposition, in an electrolyte solution, of at least one catalytic metal in the presence of a gas comprising CO 2 under electroreduction conditions onto a conductive support, wherein the at least one catalytic metal comprises copper (Cu) and is electrodeposited onto the conductive support and wherein the gas is supersaturated ( i.e .
  • the invention also relates to the process of manufacture of said catalyst compound.
  • the invention thus also relates to a process electrochemical conversion of CO 2 to small molecules.
  • CO 2 carbon dioxide
  • Cavities on the catalyst surface have also demonstrated larger selectivity for the formation of propanol thanks to the confinement of the intermediates. These examples however rely on the use of CO instead on CO 2 that are involved in the C-C dimerization step associated with the formation of multicarbon molecules.
  • CO 2 reduction reaction CO 2 reduction reaction
  • CO 2 feeds from highly concentrated sources or special CO 2 -capturing devices are required, because the low concentration of CO 2 makes it very difficult to be effectively adsorbed and activated on the surface of most catalysts, and the anaerobic atmosphere is requisite to prevent the adverse oxidation reaction from happening.
  • the Applicant has developed a new method to produce a copper based electrocatalyst compound that solves all the problems listed above.
  • the present invention deals with a new copper based electrocatalyst material, its manufacturing process and its applications, such as a method to convert CO 2 into small molecules (such as ethylene, ethanol and isopropanol) at room temperature and atmospheric pressure or higher. Being able to produce such small molecules at room temperature and atmospheric pressure in large quantities is, to the knowledge of Applicant, something that was not observed in the art.
  • the electrocatalyst material of the invention is therefore both prepared and used in CO 2 supersaturated electrolyte.
  • the Faradaic efficiency reachs a maximum of 59 % at -0.73 V versus RHE for CO 2 concentration of 3 mol L -1 under a CO 2 pressure of 10 bar.
  • the copper based electrocatalyst material of the invention is based on monometallic (Cu) crystals or dendric alloy (Ag-Cu) on a conducting support (typically a commercial carbon support such as a gas diffusion layer or a graphite foil electrode) according to the method of the invention.
  • the copper based electrocatalyst material of the invention may present a dendric morphology.
  • a first object of the invention is a method of preparing an copper based electrocatalyst material, comprising a step of in-situ electrodeposition or co-electrodeposition, in an electrolyte solution, of at least one catalytic metal in the presence of a gas comprising CO 2 under electroreduction conditions onto a conductive support, wherein
  • the at least one catalytic metal may further comprise silver (Ag).
  • the at least one catalytic metal may consist of copper and silver.
  • the atomic ratio Cu:Ag may be from 1:9 to 9.9:0.1, preferably from 7:3 to 9.8:0.2, more prefereably from 8.5:1.5 to 9.5:0.5 or even preferably 9:1.
  • the atomic ratio Cu:Ag may be tuned by adjusting the ratio of Cu and Ag precursors respectively.
  • the electrolyte solution may be a carbonated water-based electrolyte solution.
  • the carbonated water-based electrolyte is preferably chosen from CsHCO 3 , KHCO 3 and K 2 SO 4 , preferably CsHCO 3 .
  • the concentration of carbonated water-based electrolyte may be from 0.5 mol L -1 to 5.0 mol L -1 , preferably from 0.5 mol L -1 to 1.5 mol L -1 , more prefereably 1 mol L -1 .
  • the gas may comprise from 0.04 wt.% to 100 wt.% of CO 2 .
  • the gas is CO 2 .
  • the electrolyte solution is an aqueous solution.
  • the electrolyte may be supersaturated in gas.
  • the concentration of the gas, in the electrolyte solution may be from 0.05 to 7.5 mol L -1 , while gas pressure may be up to 25 bar in the reactor.
  • the gas concentration may depend on the pressure and the temperature applied to the electrolyte solution.
  • the concentration may thus be from 0.05 to 0.3 mol L -1 , at atmospheric pressure (1 ATM), at a temperature from 15 to 25°C.
  • the concentration may be from > 0.3 to 7.5 mol L -1 , at a pressure from > 1 bar to 25 bar, at a temperature from 15 to 25°C.
  • the concentration of the gas is preferably maintained constant by continuous gas injection in the electrolyte during the step of in-situ electrodeposition or co-electrodeposition.
  • the conductive support may be a carbon based conductive support.
  • the conductive support may be a gas diffusion layer (GDL) or a graphite foil electrode.
  • the conductive support may be hydrophilic.
  • the method according to the invention may thus further comprise a step of hydrophilic pre-treatment of the conductive support followe by the step of in-situ electrodeposition or co-electrodeposition.
  • the electrodeposition or co-electrodeposition is provided under a voltage of -0.80 to -2.20 V vs. Ag / AgCI (KCI saturated).
  • the electrodeposition or co-electrodeposition may be provided under a current density from 1 mA cm -2 to 50 mA cm -2 , preferably from 10 mA cm -2 to 20 mA cm -2 , for total charge of 30 C corresponding to a loading amount of 5 mg cm -2 .
  • the electrodeposition or co-electrodeposition may be provided under a current density of from 1.0 to 20.0 mA cm -2 .
  • Copper (Cu) and the optional at least one further catalytic metal (Ag) may be electrodeposited (or co-electrodeposited) using a current density from 1.0 mA cm -2 to 20 mA cm -2 , preferably from 5 mA cm -2 to 15 mA cm -2 , preferably 10 mA cm -2 .
  • the quantity of deposited silver and optional at least one further catalytic metal (Cu) may be from 0.5 C cm -2 to 50 C cm -2 , preferably from 15 C cm -2 to 35 C cm -2 .
  • the quantity of deposited Cu and optional Ag may be comprised from 15 C cm -2 to 35 C cm -2 , and more preferably from 20 C cm -2 to 30 C cm -2 .
  • the source of silver (Ag) may be AgNO 3 or CH 3 COOAg, preferably AgNO 3 .
  • the source of copper (Cu) may be CuSO 4 and Cu(NO 3 ) 2 , preferably CuSO 4 .
  • the electrodeposition or co-electrodeposition of copper and the optional at least one further catalytic metal (Ag) may be done using a carbon based-gas diffusion layer (GDL), a Pt plate, and Ag/AgCl (saturated with KCI) respectively as the working, counter, and reference electrodes, respectively.
  • the process can be done using a 2-electrode configuration using a carbon-based gas diffusion layer (GDL) and a Pt plate respectively as the working and counter electrodes, respectively.
  • the invention also relates to a copper based electrocatalyst material obtained according to the method of the invention.
  • the copper based electrocatalyst material may comprise at least one catalytic material and a conductive support.
  • the at least one catalytic metal may be in the form of a monometallic crystal or dendric alloy.
  • the at least one catalytic metal may be in the form of a metallic layer.
  • the layer of monometallic crystal or dendric alloy on the conductive support may have a thickness from 5.0 to 15.0 ⁇ m. The thickness may depend on the loading amount of the catalyst and the skilled person may adapt depending on the application.
  • the invention also relates to a process of conversion of CO 2 into small molecules, such as ethylene, ethanol and isopropanol, comprising a step of contacting CO 2 (gas) with a copper based electrocatalyst material according to the invention.
  • the conversion reaction of CO 2 may be done in a supersaturated electrolyte by the use of an applied CO 2 pressure ranging from 1.0 bar to 25.0 bar and at a temperature from 15 to 40°C, with CO 2 (gas) at a concentration from 0.05 to 7.5 mol L -1 .
  • the CO 2 concentration may depend on the pressure and the temperature applied to the electrolyte solution. Under atmospheric pressure, the concentration may thus be from 0.05 to 0.3 mol L -1 , at a temperature from 15 to 25°C.
  • the concentration may be from > 0.3 to 7.5 mol L -1 , at a pressure from > 1 bar to 25 bar, at a temperature from 15 to 25°C.
  • the concentration of the CO 2 is preferably maintained constant by continuous gas injection in the electrolyte during the step of in-situ electrodeposition or co-electrodeposition.
  • the electrolyte is a carbonated water-based electrolyte.
  • the carbonated water-based electrolyte is preferably chosen from CsHCO 3 , KHCO 3 and K 2 SO 4 , preferably CsHCO 3 .
  • the concentration of the carbonated water-based electrolyte may be from 0.5 mol L -1 to 5.0 mol L -1 , preferably from 0.5 mol L -1 to 1.5 mol L -1 , more preferably 1 mol L -1 .
  • the invention further relates to the use of the copper based electrocatalyst material according to the invention as a catalyst, preferably to convert CO 2 into small molecules. It is meant by small molecules, molecules such as CO, CH 4 , C 2 H 4 , C 2 H 5 OH and isopropanol.
  • Example 1 Preparation of an electrocatalyst material 1 (EM1) according to the invention
  • GDL hydrophilic pre-treated gas diffusion layer
  • a 0.2 mol L -1 CuSO 4 ⁇ 5H 2 O and 2 mmol L -1 AgNO 3 mixture saturated with CO 2 was applied as the electrolyte.
  • the conditions of pressure and temperature are the following:
  • the electrolyte was supersatured with CO 2 during the deposition with a CO 2 concentration of 0.3 mol L -1 .
  • the electrodeposition on GDL was performed at a current density of 1.0 and 10 mA cm -2 at room temperature for the total charge of 30 C corresponding to a loading amount of 5 mg cm -2 ( Figure 1a,b ).
  • the electrolyte was rinsed with deionized water three times immediately to avoid the further galvanic reaction.
  • the prepared electrode was dried under Ar at room temperature and store for further measurement.
  • the structure of CuAg alloy is cubic-like when CO 2 oversaturate is applied during the deposition with a deposition current density of 1.0 mA cm -2 .
  • With a deposition current density 10.0 mA cm -2 the structure of CuAg alloy is denditric ( Figure 1d ).
  • Example 2 Preparation of an electrocatalyst material CE1 (not according to the invention)
  • the conditions of pressure and temperature are the following:
  • the electrodeposited on GDL was applied at a current density of 10 mA cm -2 for the total charge of 30 C corresponding to a loading amount of 5 mg cm -2 .
  • the redundant electrolyte was rinsed with deionized water three times immediately to avoid the further galvanic reaction.
  • the prepared electrode was dried under Ar flow at room temperature for further measurement.
  • Example 3 Comparison of the performances of the electrocatalyst materials 1 (EM1) and counter-example 1 (CE1)
  • the electrolyte solution was supersaturated with CO 2 gas to reach a concentration of 0.3 mol L -1 .
  • the concentration of the electrolyte was further increased. As shown in Figure 5 , when increased the concentration of the electrolyte from 1.0 mol L -1 CsHCO 3 to 5.0 mol L -1 CsHCO 3 , the FE of isopropanol is not increasing along with the increase of the concentration of Cs + . These results reveal that the 1.0 mol L -1 Cs + is the best parameter for adjusting the Cs + concentration with CO 2 supersaturated electrolyte.
  • a customed-designed high-pressure CO 2 electrolyzer was then used to prepare the EM1 electrodes at higher CO 2 concentrations.
  • Using a high-pressure CO 2 electrolyzer can make the overall process to produce the multi-carbon product more efficiently at a higher current density.
  • the experiments were carried at out room temperature (20°) with a CO 2 pressure from 1 up to 25 bar corresponding to CO 2 concentration in the liquid electrolyte from 0.3 M up to 7.5 M. Such a process is indeed compatible with compressed CO 2 from the atmosphere.
  • the performance of the electrode was found to be stable over 200 hours with an average FE isopropanol of 56.08% and an average current density of around 104.71 mA cm -2 ( Figure 7 ). After 200 hours, the retention of the FE isopropanol and the current density were estimated to be 94.26% and 89.53%, respectively.
  • the stability of the CO 2 RR properties is further accompanied by high stability of the catalyst morphology and surface

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
EP22305020.4A 2022-01-11 2022-01-11 Procédé et utilisation d'un matériau d'électrocatalyseur à base de cuivre dans un électrolyte sursaturé Withdrawn EP4209619A1 (fr)

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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112501662A (zh) * 2020-12-15 2021-03-16 中南大学深圳研究院 一种应用于高效二氧化碳还原反应生成甲烷的铜纳米片的制备方法
WO2021102561A1 (fr) * 2019-11-25 2021-06-03 The Governing Council Of The University Of Toronto Valorisation de co à produits c3 à l'aide de catalyseurs d'électro-réduction multi-métalliques dotés de sites actifs asymétriques

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2021102561A1 (fr) * 2019-11-25 2021-06-03 The Governing Council Of The University Of Toronto Valorisation de co à produits c3 à l'aide de catalyseurs d'électro-réduction multi-métalliques dotés de sites actifs asymétriques
CN112501662A (zh) * 2020-12-15 2021-03-16 中南大学深圳研究院 一种应用于高效二氧化碳还原反应生成甲烷的铜纳米片的制备方法

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Title
BAGGER AJU WVARELA A S ET AL.: "Electrochemical C0 reduction: a classification problem[J", CHEMPHYSCHEM, vol. 18, no. 22, 2017, pages 3266 - 3273
CHUANG H C ET AL: "Material characterization in TSV fabricated by supercritical carbon dioxide electroplating", 2018 INTERNATIONAL CONFERENCE ON ELECTRONICS PACKAGING AND IMAPS ALL ASIA CONFERENCE (ICEP-IAAC), JAPAN INSTITUTE OF ELECTRONICS PACKAGING, 17 April 2018 (2018-04-17), pages 506 - 508, XP033354221, DOI: 10.23919/ICEP.2018.8374357 *
GANESAN MUTHUSANKAR ET AL: "Post-supercritical CO2 electrodeposition approach for Ni-Cu alloy fabrication: An innovative eco-friendly strategy for high-performance corrosion resistance with durability", APPLIED SURFACE SCIENCE, vol. 577, 18 November 2021 (2021-11-18), AMSTERDAM, NL, pages 151955, XP055929387, ISSN: 0169-4332, DOI: 10.1016/j.apsusc.2021.151955 *
HERNANDEZ SFARKHONDEHFAL M ASASTRE F ET AL.: "Syngas production from electrochemical reduction of C0 : current status and prospective implementation[J", GREEN CHEMISTRY, vol. 19, no. 10, 2017, pages 2326 - 2346
HORI YWAKEBE HTSUKAMOTO T ET AL.: "Electrocatalytic process of CO selectivity in electrochemical reduction of C0 at metal electrodes in aqueous media[J", ELECTROCHIMICA ACTA, vol. 39, 1994, pages 1833 - 1839, XP026551584, DOI: 10.1016/0013-4686(94)85172-7
WHIPPLE D TKENIS P J A: "Prospects of C02 utilization via direct heterogeneous electrochemical reduction[J", THE JOURNAL OF PHYSICAL CHEMISTRY LETTERS, vol. 1, no. 24, 2010, pages 3451 - 3458, XP055599832, DOI: 10.1021/jz1012627
XIA CZHU PJIANG Q ET AL.: "Continuous production of pure liquid fuel solutions via electrocatalytic C0 reduction using solid-electrolyte devices[J", NATURE ENERGY, vol. 4, no. 9, 2019, pages 776 - 785

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