WO2017176600A1 - Procédé électrocatalytique permettant la conversion de dioxyde de carbone - Google Patents

Procédé électrocatalytique permettant la conversion de dioxyde de carbone Download PDF

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WO2017176600A1
WO2017176600A1 PCT/US2017/025630 US2017025630W WO2017176600A1 WO 2017176600 A1 WO2017176600 A1 WO 2017176600A1 US 2017025630 W US2017025630 W US 2017025630W WO 2017176600 A1 WO2017176600 A1 WO 2017176600A1
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polymer
cell
active element
catalytically active
reaction
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PCT/US2017/025630
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English (en)
Inventor
Richard I. Masel
Amin Salehi-Khojin
Robert Kutz
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Dioxide Materials, Inc.
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Priority claimed from US15/090,477 external-priority patent/US9580824B2/en
Priority claimed from US15/158,227 external-priority patent/US9945040B2/en
Priority claimed from US15/400,712 external-priority patent/US9815021B2/en
Application filed by Dioxide Materials, Inc. filed Critical Dioxide Materials, Inc.
Publication of WO2017176600A1 publication Critical patent/WO2017176600A1/fr

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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
    • 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
    • C25B11/04—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
    • C25B11/091—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of at least one catalytic element and at least one catalytic compound; consisting of two or more catalytic elements or catalytic compounds
    • C25B11/095—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of at least one catalytic element and at least one catalytic compound; consisting of two or more catalytic elements or catalytic compounds at least one of the compounds being organic
    • 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 field of the invention is electrocatalysis and electrocatalysts.
  • the catalysts of this invention are applicable, for example, to the electrochemical conversion of carbon dioxide into useful products.
  • an electrochemical cell contains an anode 50, a cathode 51 and an electrolyte 53 as illustrated in FIG. 1. Catalysts are placed on the anode, and/or the cathode, and/or in the electrolyte to promote desired chemical reactions. During operation, reactants or a solution containing reactants is fed into the cell. Then a voltage is applied between the anode and the cathode, to promote an electrochemical reaction.
  • catalysts comprising one or more of V, Cr, Mn, Fe, Co, Ni, Cu, Sn, Zr, Nb, Mo, Ru, Rh, Pd, Ag, Cd, Hf, Ta, W, Re, Ir, Pt, Au, Hg, Al, Si, In, Tl, Pb, Bi, Sb, Te, U, Sm, Tb, La, Ce, and Nd have all shown activity for CO2 conversion.
  • Reviews include Hori (Modern Aspects of Electrochemistry, 42, 89-189, 2008) ("the Hori Review"), Gattrell, et al.
  • the catalysts have been in the form of either bulk materials, supported particles, collections of particles, small metal ions or organometallics. Still, according to Bell (A. Bell. Ed, Basic Research Needs, Catalysis For Energy, U.S. Department of Energy Report PNNL17712, 2008) ("the Bell Report"), "The major obstacle preventing efficient conversion of carbon dioxide into energy -bearing products is the lack of catalyst" with sufficient activity at low overpotentials and high electron conversion efficiencies.
  • the overpotential is associated with lost energy of the process, so the overpotential should be as low as possible. Yet, according to The Bell Report "Electron conversion efficiencies of greater than 50 percent can be obtained, but at the expense of very high overpotentials". This limitation needs to be overcome before practical processes can be obtained.
  • a second disadvantage of many of the catalysts is that they also have low electron conversion efficiency. Catalyst systems are considered practical where electron conversion is over 50%.
  • PCT/US2011/030098 published as WO2011/120021
  • PCT/US2011/042809 published as WO2012/006240
  • a catalyst mixture containing an active metal and a Helper Catalyst could catalyze CCh conversions with low overpotential and high electron conversion efficiency.
  • the catalysts disclosed in these patent applications showed a lower activity than was desired.
  • the present process employs a novel catalyst combination that can overcome one or more of the limitations of low rates, high overpotentials and low electron conversion efficiencies (namely, selectivities), low rates for catalytic reactions and high power requirements for sensors.
  • the catalyst combination or mixture includes at least one Catalytically Active Element in the form of supported or unsupported particles wherein the particles have an average particle size (as defined below) between about 0.6 nm and 100 nm, preferably between 0.6 nm and 40 nm, and most preferable between 0.6 nm and 10 nm.
  • the catalyst combination also includes a Helper Polymer that can contain, for example, positively charged cyclic amine groups, such as imidazoliums or pyridiniums.
  • the catalyst combination of a Catalytically Active Element and a Helper Polymer are useful, for example, in the cathode catalyst layer of an electrochemical cell used for conversion of CO2 to various reaction products.
  • the present process is not limited to catalysts for CO2 conversion.
  • catalysts that include Catalytically Active Elements and Helper Catalysts or Helper Polymers might enhance the rate of a wide variety of chemical reactions.
  • Reaction types include:
  • FIG. 1 is a diagram of a typical electrochemical cell.
  • FIG. 2 illustrates how the cyclic voltammogram (CV) of electrochemical water reduction varies with the average particle size of the Catalytically Active Element silver on the cathode: (A) bare silver electrode, (B) electrode covered by nominally 200 nm silver particles, (C) electrode covered by nominally 100 nm silver particles, (D) electrode covered by nominally 20-40 nm silver particles, (E) electrode covered by 5 nm silver particles, and (F) electrode covered by 0.67 nm silver particles.
  • the numeric designations 500-505 indicate the positions of the hydrogen peak in the figures. All of the CV's are reported as the current divided by the electrochemical surface area of the particles
  • FIG. 3 illustrates how the CV changes in FIG. 2 when CO2 is added to the reaction: (A) bare silver electrode, (B) electrode covered by nominally 200 nm silver particles, (C) electrode covered by nominally 100 nm silver particles, (D) electrode covered by nominally 20-40 nm silver particles, (E) electrode covered by 5 nm silver particles, and (F) electrode covered by 0.67 nm silver particles.
  • the numeric designations 600-605 indicate the CO2 reduction peak in the figures. All of the CV's are reported as the current divided by the electrochemical surface area of the particles
  • FIG. 4 illustrates particle size distribution of the (A) nominally 20-40 nm silver particles, (B) nominally 100 nm silver particles, and (C) nominally 200 nm silver particles as measured by dynamic light scattering.
  • the nominally 20-40 nm particles have an average size of 35 nm.
  • the nominally 100 nm particles have an average size of 70 nm and the nominally 200 nm particles have an average size of 190 nm.
  • FIG. 5 shows how the voltammograms of a 5 cm 2 cell change when 0% (plot 200), 1 % (plot 201), 5% (plot 202), and 10% (plot 203) of Helper Polymer PSMIMC1 are added to the CC electrolyzer cathode catalyst layer, where the percentage is calculated as the weight of the PSMIMC1 divided by the weight of the silver.
  • PSMIMC1 refers to the chloride form of a co-polymer of polystyrene and poly l-(p-vinylbenzyl)-3-methyl-imidazolium.
  • any numerical value ranges recited herein include all values from the lower value to the upper value in increments of one unit provided that there is a separation of at least two units between any lower value and any higher value.
  • concentration of a component or value of a process variable such as, for example, size, angle size, pressure, time and the like, is, for example, from 1 to 90, specifically from 20 to 80, more specifically from 30 to 70, it is intended that values such as 15 to 85, 22 to 68, 43 to 51 , 30 to 32, and so on, are expressly enumerated in this specification.
  • one unit is considered to be 0.0001, 0.001, 0.01 or 0.1 as appropriate.
  • CV refers to a cyclic voltammogram or cyclic voltammetry.
  • Cathode Overpotential refers to the overpotential on the cathode of an electrochemical cell.
  • Anode Overpotential refers to the overpotential on the anode of an electrochemical cell.
  • Electrode Conversion Efficiency refers to selectivity of an electrochemical reaction. More precisely, it is defined as the fraction of the current that is supplied to the cell that goes to the production of a desired product.
  • Catalytically Active Element refers to any chemical element that can serve as a catalyst for the electrochemical conversion of CO2.
  • Helper Catalyst refers to any organic molecule or ion, or a mixture of organic molecules and/or ions, that does at least one of the following:
  • Helper Polymer refers to a polymer that does at least one of the following: (a) Speeds up a chemical reaction;
  • MEA membrane electrode assembly
  • imidazolium refers to a positively charged ligand containing an imidazole group. This includes a bare imidazole or a substituted imidazole.
  • Ri- R.5 are each independently selected from hydrogen, halogens, linear alkyls, branched alkyls, cyclic alkyls, heteroalkyls, aryls, cyclic aryls, heteroaryls, alkylaryls, heteroalkylaryls, and polymers thereof, such as the vinyl benzyl copolymers described herein, are specifically included.
  • pyridinium refers to a positively charged ligand containing a pyridinium group. This includes a protonated bare pyridine or a substituted pyridine or pyridinium.
  • R.6-R11 are each independently selected from hydrogen, halogens, linear alkyls, branched alkyls, cyclic alkyls, heteroalkyls, aryls, cyclic aryls, heteroaryls, alkylaryls, heteroalkylaryls, and polymers thereof, such as the vinyl benzyl copolymers described herein, are specifically included.
  • pyrazoliums refers to a positively charged ligand containing a pyrazolium group. This includes a bare pyrazolium or a substituted pyrazolium.
  • R16-R20 are each independently selected from hydrogen, halogens, linear alkyls, branched alkyls, cyclic alkyls, heteroalkyls, aryls, cyclic aryls, heteroaryls, alkylaryls, heteroalkylaryls, and polymers thereof, such as the vinyl benzyl copolymers described herein, are specifically included.
  • phosphonium refers to a positively charged ligand containing phosphorous. This includes substituted phosphorous.
  • R12-R15 are each independently selected from hydrogen, halogens, linear alkyls, branched alkyls, cyclic alkyls, heteroalkyls, aryls, cyclic aryls, heteroaryls, alkylaryls, heteroalkylaryls, and polymers thereof, such as the vinyl benzyl copolymers described herein, are specifically included.
  • positively charged cyclic amine refers to a positively charged ligand containing a cyclic amine. This specifically includes imidazoliums, pyridiniums, pyrazoliums, pyrrolidiniums, pyrroliums, pyrimidiums, piperidiniums, indoliums, triaziniums, and polymers thereof, such as the vinyl benzyl copolymers described herein.
  • the present process relates generally to Catalytically Active Element, Helper Polymer Mixtures where the mixture does at least one of the following:
  • such mixtures can increase the rate of CO2 conversion to a value that is higher than when the same Catalytically Active Element is used without the Helper Polymer.
  • PCT/US2011/030098 published as WO2011/120021
  • PCT/US2011/042809 published as WO2012/006240
  • Active Metals included one or more of V, Cr, Mn, Fe, Co, Ni, Cu, Sn, Zr, Nb, Mo, Ru, Rh, Pd, Ag, Cd, Hf, Ta, W, Re, Ir, Pt, Au, Hg, Al, Si, In, Tl, Pb, Bi, Sb, Te, U, Sm, Tb, La, Ce, and Nd.
  • Helper Polymers include polymers containing one or more of positively charged cyclic amines, phosphines, imidazoliums, pyridiniums, pyrrolidiniums, phosphoniums, sulfoniums, prolinates, methioninates, cholines,
  • acetylcholines alanines, aminoacetonitriles, methylammoniums, arginines, aspartic acids, threonines, chloroformamidiniums, thiouroniums, quinoliniums, pyrrolidinols, serinols, benzamidines, sulfamates, acetates, carbamates, triflates, and cyanides.
  • a voltage of 1 V is applied to the cell without the polymer P, and then the voltage is raised to a voltage V such that the output current is as least 20 niA/cm 2 .
  • the current output of the cell is recorded after running for 30 minutes.
  • the polymer P is a Helper Polymer for that reaction.
  • the two MEA's are manufactured as follows:
  • a solvent S is identified such that S can dissolve at least 5 mg of the polymer P in 3 mL of solution.
  • a cathode for the MEA containing the polymer P is produced as follows:
  • the ink is painted onto a gas diffusion layer (Sigracet 35 BC GDL, Ion Power Inc., New Castle, DE) covering an area of 6 cm x 6 cm.
  • the electrode was immersed in 1 M KOH for at least 1 hour for ion exchange, then the electrode is cut into 2.5 cm x 2.5 cm sections for cell testing.
  • the anode for the MEA is produced prepared as follows:
  • the ink is painted onto 6 cm x 6 cm of carbon fiber paper (Toray Paper 120, Fuel Cell Earth, Woburn, MA).
  • the IrC loading is about 2 mg/cm 2
  • the electrode is cut into 3 cm x 3 cm sections for cell testing.
  • anion exchange membrane is sandwiched between the anode and the cathode with the metal-containing layers on the anode and cathode facing the membrane to create the MEA.
  • the anion exchange membrane is one of the helper membranes described in US9,370,773.
  • the catalyst of the present application was prepared by modifying the structure of the silver so it is more active.
  • the catalyst can be in the form of supported or unsupported metal particles wherein the average particle size is below about 100 nm, preferably between 0.6 nm and 40 nm, more preferably between 0.6 nm and 20 nm, and most preferably between 0.6 nm and 10 nm.
  • the particle sizes can be determined by one or more of microscopy, x- ray line broadening, chemisorption, or small angle x-ray scattering. For example, one might measure the x-ray diffraction partem of the catalysts, determine ⁇ , the width of the diffraction line at some angle ⁇ , and then calculate the particle size, D, from the Scherrer equation:
  • ⁇ is the wavelength of the x-ray beam.
  • Chemisorption can alternately be used to measure the Sg, the surface area of the active element per unit mass, and then calculate the particle size from the formula:
  • the present process specifically includes any catalyst with a particle size between 0.6 nm and 100 nm measured by any of x-ray line broadening, chemisorption, or small angle x- ray scattering.
  • This example illustrates the effect of silver particle size on the rate of CCh conversion on an EMIM-BF4 (Sigma Aldrich, St. Louis, MO) coated silver catalyst.
  • a silver ink was deposited onto a silver rotating disk electrode (Pine Instruments, Grove City, PA).
  • the silver electrode was polished, and a CV was run as described in the fourth paragraph below.
  • Subsequent experiments were run by depositing one of: (i) 200 nm silver (Sigma Aldrich, St. Louis, MO); (ii) 100 nm silver (Sigma Aldrich); (iii) 20-40 nm silver (Sigma Aldrich); (iv) 5 nm (UT Dots, Champaign, IL); (v) 0.67 nm (Purest Colloids, Westampton, NJ) onto the silver electrode and running the CV as set forth in the fourth paragraph below.
  • a silver ink was prepared by mixing 5.6 mg of silver particles with 1 ml deoxygenated Millipore water.
  • the catalyst was applied on the surface of a rotating electrode by adding 60 of the ink to the surface and allowing the water to evaporate under ambient temperature for 60 minutes. In order to ensure the quality of the measurements, special attention was paid to the material cleaning and solution purity.
  • the 10 nm Ag arrived suspended in an organic solution, so this solution was applied to the silver electrode, and subsequently heated in air at 85°C for 3 hours to remove residual organics.
  • the 0.6 nm Ag particles arrived suspended in distilled water, so they were used as received.
  • the counter electrode was made by attaching a 25 mm x 25 mm platinum mesh (size 52) to a 5-inch platinum wire (99.9%, 0.004-inch diameter).
  • a silver quasi-reference electrode (Ag-QRE) was used.
  • the electrolytes were first loaded into the glass cell and then purged with dry argon (99.99%) for two hours in order to remove oxygen from the electrolytes.
  • a 20-40 linear sweep cyclic voltammogram at 75 mVs " 1 was taken with the range between -2 V and 0 vs. Ag-QRE in order to condition the electrodes and remove oxides from the surfaces.
  • FIG. 2 shows how the CV of water varies with particle size.
  • FIG. 3 shows how the CV changes when CO2 is added to the electrochemical cell. Notice that CO2 conversion peaks, labeled 100, 101, 102, 103, 104, 105 and 106 are observed. The CCh conversion peaks grow as one decreases the particle size from 1000-10 nm, but then we observed the opposite effect, where the CCh peak shrinks moving from 10 nm to 0.6 nm. Evidently, there is an optimal particle size somewhere between 0.6 and 100 nm. The optimal size is probably between 0.6 and 40 nm, most probably between 0.6 and 20 nm.
  • V, Cr, Mn, Fe, Co, Ni, Cu, Zr, Nb, Mo, Ru, Rh, Pd, Ag, Cd, W, Re, Ir, Pt, Au, Hg, Pb, Bi, electrocatalysts for CO2 conversion should have an optimal size between 0.6 and 100 nm.
  • the objective of this example is to show that polymers containing imidazoliums can be Helper Catalysts.
  • PSMIM polystyrene and poly l-(p-vinylbenzyl)-3-meth l-imidazolium:
  • the inhibitor-free styrene was prepared by passing styrene (Sigma- Aldrich) through the tert-butylcatechol (TBC) inhibitor remover (Sigma- Aldrich 311340). In general, 40 ml of remover is sufficient to yield 50 ml of clear, inhibitor free styrene. Inhibitor TBC in 4- vinylbenzyl chloride (4-VBC) was removed by the same inhibitor remover in a similar fashion.
  • TBC tert-butylcatechol
  • 4-VBC 4- vinylbenzyl chloride
  • Poly(4-vinylbenzyl chloride-co-styrene) was then synthesized by heating a solution of inhibitor-free styrene (Sigma- Aldrich) (36.139 g, 350 mmol) and 4-vinylbenzyl chloride (Sigma-Aldrich) (29.7272 g, 190 mmol) in chlorobenzene (Sigma-Aldrich) (45 ml) at 60- 65°C in an oil bath for approximately 20 hours under argon gas with AIBN ( ⁇ , ⁇ '- Azoisobutyronitrile, Sigma-Aldrich) (0.5927 g, 0.90 wt% based on the total monomers' weight) as initiator.
  • AIBN ⁇ , ⁇ '- Azoisobutyronitrile, Sigma-Aldrich
  • Polystyrene methyimidazolium chloride (PSMIM-C1) was synthesized by adding 1-methylimidazole (Sigma-Aldrich) (2.8650 g, 034.9 mmol), which is an alkylimidazole, to the solution of the poly(4-VBC-co-St) (5.0034 g, 19.4 mmol) in anhydrous NN- Dimethylformamide (DMF) (Sigma-Aldrich) (30 mL). The mixture was then stirred at around 30°C for around 50 hours to form a PSMIM solution.
  • 1-methylimidazole Sigma-Aldrich
  • DMF Dimethylformamide
  • Anion exchange membrane polymer PSMIM-DVB was synthesized starting with poly(4-vinylbenzyl chloride co-styrene.) 1-methylimidazole (Sigma-Aldrich) (3.912 g, 47.7 mmol) was added in a 250 ml 3-neck round bottom flask to the solution of the poly(4-VBC- co-St) (15.358 g, 59.8mmol) in anhydrous ⁇ , ⁇ -Dimethylformamide (DMF) (Sigma-Aldrich) (105 ml).
  • DMF ⁇ , ⁇ -Dimethylformamide
  • Membranes were prepared by casting the PSMIM-DVB solution prepared above directly onto a flat glass surface. The thickness of the solution on the glass was controlled by a film applicator (MTI Corporation, Richmond, CA) with an adjustable doctor blade. The membranes were then dried in a vacuum oven in the following stepwise fashion. They were first kept at 80°C for 120 minutes, then at 100°C for 60 minutes, at 120°C for 30 minutes and finally at 150°C for 60 minutes. Chloride ions in the membranes were removed by soaking the membranes in 1 M KOH solution for 24 hours or longer.
  • the cathode layer in Example 1 was prepared as follows. Silver ink was made by mixing 100 mg of silver nanoparticles (20-40 nm, 45509, Alfa Aesar, Ward Hill, MA), 5 mg porous carbon (Vulcan XC-72R, Fuel Cell Earth, Woburn, MA) and different amounts of PSMIM-C1 in 3 ml of ethanol (459844, Sigma-Aldrich). The mixture was then sonicated for 10 minutes. The silver ink was painted onto a gas diffusion layer (Sigracet 35 BC GDL, Ion Power Inc., New Castle, DE) covering an area of 6 cm x 6 cm. The electrode was immersed in 1 M KOH for at least 1 hour so that PSMIM-C1 converted by ion exchange to PSMIM-OH. Then the electrode was cut into 2.5 cm x 2.5 cm sections for cell testing.
  • Silver ink was made by mixing 100 mg of silver nanoparticles (20-40 nm, 45509, Alfa Aesar, Ward Hill, MA), 5 mg
  • Example 1 The anode in Example 1 was prepared as follows: 100 mg of IrCh (43396, Alfa Aesar) was dispersed in the mixture of 1 ml of deionized water, 2 ml of isopropanol (3032-16, Cell Fine Chemicals, Avantor Performance Materials, Center Valley, PA) and 0.1 ml of 5 wt.% poly-tetrafluoroethylene (PTFE) dispersion (665800, Sigma-Aldrich). The mixture was sonicated for 10 min using a water bath sonicator. The ink was painted onto 6 cm x 6 cm of carbon fiber paper (Toray Paper 120, Fuel Cell Earth). The actual IrCh loading was about 2 mg/cm 2 The electrode was cut into 3 cm x 3 cm sections for cell testing.
  • IrCh 43396, Alfa Aesar
  • the PSMIM-DVB membrane was sandwiched between the anode and the cathode with the metal-containing layers on the anode and cathode facing the membrane, and the whole assembly was mounted in a Fuel Cell Technologies 5 cm 2 fuel cell hardware assembly with serpentine flow fields.
  • CCh humidified at 25°C was fed into the cathode flow field at a rate of 20 seem, and 10 mM KHCO3 was fed into the anode flow field.
  • the cyclic voltammograms were collected by scanning the cell voltage from 1.2 to 3.0 V. All of the scans were made at room
  • FIG. 5 shows the results of the above scans.
  • Plot 200 is a base case with no PSMIM in the cathode catalyst layer ink. It should be noted that the current increases when PSMIM is added to the catalyst layer in a later sample, such that the PSMIM weight is 1% of the weight of the silver (plot 201). Further increases in the current are seen as the PSMIM concentration is increased so that the PSMIM weight is 5% of the weight of the silver (plot 202). Then there is a small decrease when the weight of the PSMIM is increased to 10% of the weight of the silver (plot 203).
  • Co-pending U.S. patent application Serial No. 15/158,227 provides a number of other examples.
  • the data in the '227 application indicates that polymers containing positively charged cyclic amines can also act as Helper Polymers.

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Abstract

L'invention concerne un procédé électrocatalytique permettant la conversion de dioxyde de carbone, consistant à combiner un élément catalytiquement actif et un polymère auxiliaire en présence de dioxyde de carbone, à laisser une réaction se produire pour produire un produit de réaction, et à appliquer de l'énergie électrique à ladite réaction pour réaliser la conversion électrochimique dudit réactif dioxyde de carbone dans ledit produit de réaction. L'élément catalytiquement actif peut être un métal sous la forme de particules ou paillettes supportées ou non supportées ayant une taille moyenne comprise entre 0,6 nm et 100 nm. Le produit de réaction en comprend au moins un parmi CO, HCO−, H2CO, (HCO2)−, H2CO2, CH3OH, CH4, C2H4, CH3CH2OH, CH3COO−, CH3COOH, C2H6, (COOH)2, (COO−)2 et CF3COOH.
PCT/US2017/025630 2016-04-04 2017-03-31 Procédé électrocatalytique permettant la conversion de dioxyde de carbone WO2017176600A1 (fr)

Applications Claiming Priority (6)

Application Number Priority Date Filing Date Title
US15/090,477 US9580824B2 (en) 2010-07-04 2016-04-04 Ion-conducting membranes
US15/090,477 2016-04-04
US15/158,227 2016-05-18
US15/158,227 US9945040B2 (en) 2010-07-04 2016-05-18 Catalyst layers and electrolyzers
US15/400,712 US9815021B2 (en) 2010-03-26 2017-01-06 Electrocatalytic process for carbon dioxide conversion
US15/400,712 2017-01-06

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110376263A (zh) * 2019-06-17 2019-10-25 贾晨晓 一种用于检测水果成熟的检测装置及其方法
WO2020240218A1 (fr) 2019-05-25 2020-12-03 Szegedi Tudományegyetem Cellule d'électrolyseur modulaire et procédé de conversion de dioxyde de carbone en produits gazeux à pression élevée et à taux de conversion élevé
US11718921B2 (en) 2018-08-20 2023-08-08 Thalesnano Zrt Modular electrolyzer unit to generate gaseous hydrogen at high pressure and with high purity

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