EP4010513A1 - Process for forming and regenerating a copper cathode for an electrochemical cell and electrochemical cell for the production of industrial products - Google Patents
Process for forming and regenerating a copper cathode for an electrochemical cell and electrochemical cell for the production of industrial productsInfo
- Publication number
- EP4010513A1 EP4010513A1 EP20761314.2A EP20761314A EP4010513A1 EP 4010513 A1 EP4010513 A1 EP 4010513A1 EP 20761314 A EP20761314 A EP 20761314A EP 4010513 A1 EP4010513 A1 EP 4010513A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- substrate
- copper
- electrochemical cell
- process according
- cathode
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 70
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 65
- 239000010949 copper Substances 0.000 title claims abstract description 65
- 238000000034 method Methods 0.000 title claims abstract description 56
- 230000008569 process Effects 0.000 title claims abstract description 51
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 22
- 230000001172 regenerating effect Effects 0.000 title claims abstract description 18
- 239000000758 substrate Substances 0.000 claims abstract description 81
- 230000009467 reduction Effects 0.000 claims abstract description 38
- 238000007743 anodising Methods 0.000 claims abstract description 13
- 230000003197 catalytic effect Effects 0.000 claims abstract description 12
- 230000002378 acidificating effect Effects 0.000 claims abstract description 11
- 239000012224 working solution Substances 0.000 claims abstract description 10
- 239000002086 nanomaterial Substances 0.000 claims abstract description 9
- 239000000243 solution Substances 0.000 claims abstract description 7
- 150000003841 chloride salts Chemical class 0.000 claims abstract description 5
- 150000003467 sulfuric acid derivatives Chemical class 0.000 claims abstract description 5
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 55
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 31
- 239000003792 electrolyte Substances 0.000 claims description 28
- 239000001569 carbon dioxide Substances 0.000 claims description 24
- 239000000047 product Substances 0.000 claims description 23
- 239000000203 mixture Substances 0.000 claims description 15
- 229910052751 metal Inorganic materials 0.000 claims description 12
- 239000002184 metal Substances 0.000 claims description 12
- 238000000151 deposition Methods 0.000 claims description 11
- 229910000028 potassium bicarbonate Inorganic materials 0.000 claims description 11
- 239000011736 potassium bicarbonate Substances 0.000 claims description 11
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 claims description 11
- 239000003426 co-catalyst Substances 0.000 claims description 10
- 230000008021 deposition Effects 0.000 claims description 9
- 239000007789 gas Substances 0.000 claims description 9
- 235000015497 potassium bicarbonate Nutrition 0.000 claims description 9
- 238000004140 cleaning Methods 0.000 claims description 7
- 239000008151 electrolyte solution Substances 0.000 claims description 6
- 238000000605 extraction Methods 0.000 claims description 6
- 239000012528 membrane Substances 0.000 claims description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 5
- 239000007864 aqueous solution Substances 0.000 claims description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 5
- 238000005868 electrolysis reaction Methods 0.000 claims description 5
- 239000001301 oxygen Substances 0.000 claims description 5
- 229910052760 oxygen Inorganic materials 0.000 claims description 5
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 4
- 239000007853 buffer solution Substances 0.000 claims description 4
- 230000007935 neutral effect Effects 0.000 claims description 4
- 238000000746 purification Methods 0.000 claims description 4
- 239000010936 titanium Substances 0.000 claims description 4
- 229910052719 titanium Inorganic materials 0.000 claims description 4
- 230000005587 bubbling Effects 0.000 claims description 3
- 150000001879 copper Chemical class 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 3
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 claims description 3
- 229910052939 potassium sulfate Inorganic materials 0.000 claims description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 claims description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 2
- 239000007795 chemical reaction product Substances 0.000 claims description 2
- 239000008367 deionised water Substances 0.000 claims description 2
- 239000001103 potassium chloride Substances 0.000 claims description 2
- 235000011164 potassium chloride Nutrition 0.000 claims description 2
- 239000001120 potassium sulphate Substances 0.000 claims description 2
- 235000011151 potassium sulphates Nutrition 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- 238000007654 immersion Methods 0.000 claims 1
- 230000015572 biosynthetic process Effects 0.000 abstract description 7
- 238000006722 reduction reaction Methods 0.000 description 32
- 238000006243 chemical reaction Methods 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 9
- 229910002091 carbon monoxide Inorganic materials 0.000 description 9
- 238000002048 anodisation reaction Methods 0.000 description 8
- 229910052738 indium Inorganic materials 0.000 description 8
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 8
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 7
- 238000004611 spectroscopical analysis Methods 0.000 description 6
- 238000011161 development Methods 0.000 description 5
- 230000018109 developmental process Effects 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 239000000446 fuel Substances 0.000 description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- 238000006479 redox reaction Methods 0.000 description 4
- 230000008929 regeneration Effects 0.000 description 4
- 238000011069 regeneration method Methods 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 3
- 229910052737 gold Inorganic materials 0.000 description 3
- 239000010931 gold Substances 0.000 description 3
- 229930195733 hydrocarbon Natural products 0.000 description 3
- 150000002430 hydrocarbons Chemical class 0.000 description 3
- 239000007769 metal material Substances 0.000 description 3
- 229910052697 platinum Inorganic materials 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 239000011701 zinc Substances 0.000 description 3
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 229910052793 cadmium Inorganic materials 0.000 description 2
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000000970 chrono-amperometry Methods 0.000 description 2
- 230000003750 conditioning effect Effects 0.000 description 2
- 230000001419 dependent effect Effects 0.000 description 2
- 238000004070 electrodeposition Methods 0.000 description 2
- 239000006260 foam Substances 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 238000001755 magnetron sputter deposition Methods 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- -1 platinum Chemical class 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- 238000002207 thermal evaporation Methods 0.000 description 2
- 229910052718 tin Inorganic materials 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- GGZZISOUXJHYOY-UHFFFAOYSA-N 8-amino-4-hydroxynaphthalene-2-sulfonic acid Chemical compound C1=C(S(O)(=O)=O)C=C2C(N)=CC=CC2=C1O GGZZISOUXJHYOY-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- XURCIPRUUASYLR-UHFFFAOYSA-N Omeprazole sulfide Chemical compound N=1C2=CC(OC)=CC=C2NC=1SCC1=NC=C(C)C(OC)=C1C XURCIPRUUASYLR-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- JXLHNMVSKXFWAO-UHFFFAOYSA-N azane;7-fluoro-2,1,3-benzoxadiazole-4-sulfonic acid Chemical compound N.OS(=O)(=O)C1=CC=C(F)C2=NON=C12 JXLHNMVSKXFWAO-UHFFFAOYSA-N 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000007806 chemical reaction intermediate Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 230000001143 conditioned effect Effects 0.000 description 1
- HVMJUDPAXRRVQO-UHFFFAOYSA-N copper indium Chemical compound [Cu].[In] HVMJUDPAXRRVQO-UHFFFAOYSA-N 0.000 description 1
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical class Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 1
- HTXDPTMKBJXEOW-UHFFFAOYSA-N dioxoiridium Chemical compound O=[Ir]=O HTXDPTMKBJXEOW-UHFFFAOYSA-N 0.000 description 1
- 238000002848 electrochemical method Methods 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 239000008246 gaseous mixture Substances 0.000 description 1
- 239000005431 greenhouse gas Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 150000002471 indium Chemical class 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910000457 iridium oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000000386 microscopy Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000000877 morphologic effect Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 238000005289 physical deposition Methods 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 230000009919 sequestration Effects 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229910021653 sulphate ion Inorganic materials 0.000 description 1
- 238000004832 voltammetry Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- 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
- C25B11/073—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
- 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
-
- 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
-
- 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
- C25B9/00—Cells or assemblies of cells; Constructional parts of cells; Assemblies of constructional parts, e.g. electrode-diaphragm assemblies; Process-related cell features
- C25B9/17—Cells comprising dimensionally-stable non-movable electrodes; Assemblies of constructional parts thereof
- C25B9/19—Cells comprising dimensionally-stable non-movable electrodes; Assemblies of constructional parts thereof with diaphragms
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
- C25D11/02—Anodisation
- C25D11/024—Anodisation under pulsed or modulated current or potential
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
- C25D11/02—Anodisation
- C25D11/34—Anodisation of metals or alloys not provided for in groups C25D11/04 - C25D11/32
-
- 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
- C25D3/54—Electroplating: Baths therefor from solutions of metals not provided for in groups C25D3/04 - C25D3/50
-
- 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
- C25D5/34—Pretreatment of metallic surfaces to be electroplated
Definitions
- the present invention relates to a process for forming and regenerating a copper cathode for electrochemical applications.
- the invention relates to an electrochemical cell for the production of industrial products, for example syngas.
- the invention falls within the field of electrochemical devices for the production of useful molecules from an energy and industrial point of view by exploiting redox reactions which occur on the surface of the electrodes so as to develop syngas, a fundamental precursor for the industrial synthesis of hydrocarbon fuels.
- the electrochemical cells consist of an anode and a cathode immersed in an electrolyte used to transport ions resulting from the redox reactions occurring on the surface of the electrodes.
- the electrochemical cells are advantageously configured to convert electrical energy through such redox reactions, without any thermal combustion process occurring.
- the electrochemical solution is of particular interest, as it focuses on reducing the gas on the surface of an appropriate catalytic cathodic substrate.
- the electrodes may exhibit a nanostructure surface morphology to implement the efficiency of the redox exchange reactions and thus the final amperometric yield.
- the technical task underlying the present invention is to propose a process for forming and regenerating a copper cathode for an electrochemical cell and an electrochemical cell for the production of industrial products, both capable of overcoming the drawbacks of the aforementioned prior art.
- an object of the present invention is to provide a process which can be calibrated with the control of a few simple parameters (e.g., frequency and time intervals), which is functional for both forming and regenerating a copper cathode for an electrochemical cell.
- a few simple parameters e.g., frequency and time intervals
- Another object of the present invention is to provide a forming and regenerating process having an excellent CO 2 reduction efficiency in an aqueous environment.
- an object of the present invention is to provide an electrochemical or electrolytic cell capable of operating in environmentally compatible conditions.
- Another object of the present invention is to provide an electrochemical or electrolytic cell produced with materials of simple availability, low cost and low environmental impact.
- a further object of the present invention is to provide an electrochemical or electrolytic cell compatible with use in conjunction with a renewable energy source, such as photovoltaics, for the storage of electrical energy in the form of industrial products.
- the specified technical task and the specified objects are substantially achieved by a process for forming and regenerating a copper cathode for an electrochemical cell and an electrochemical cell for the production of industrial products, interesting from an energy point of view (as they can be used to obtain hydrocarbons), which comprise the technical characteristics set out in the independent claims.
- the dependent claims correspond to further advantageous aspects of the invention.
- the invention relates to a process for forming and regenerating a copper cathode for an electrochemical cell for the production of industrial products, for example syngas.
- Such process comprises the operating steps of: preparing a copper substrate defining an electrode; anodising the substrate in an electrolytic solution based on sulphates and chlorides for a period of at least 1 minute, at an AC electric potential varying between 0 mV (millivolt) and +2000 mV and with a frequency varying between 100 Hz (Hertz) and 1500 Hz.
- the anodisation is also carried out at atmospheric pressure and ambient temperature so that copper salts form and can be deposited on an active surface of the substrate; carrying out an electrochemical reduction of the anodised substrate in an electrolytic working solution having a non-acidic pH, so that catalytic neutral copper nanostructures having a variable density depending on the parameters used form on the active surface, so as to obtain cell current densities between about 50 mA/cm 2 (milliAmps/square centimetre) and 200 mA/cm 2 at an operating potential of about -1500 mV.
- the surface density of the copper nanocubes varies between 1 - 2 nanocubes per mm 2 (square micrometre) and about ten nanocubes per mm 2 associated in agglomerates and columnar structures.
- the nanostructuring of a catalytic surface makes it possible to significantly modify the efficiency and selectivity of the same material with respect to the different reaction products, as well as allow the exposure of an electrochemically active surface greater than a planar geometry or "bulk” interface.
- the result of the process is a copper cathode having catalytic activity which is extremely sensitive to the interface structure on which the various reaction intermediates coordinate, so as to make the nanostructured material radically different from the initial material.
- the invention relates to an electrochemical cell for the production of industrial products, which comprises a box-like body having a containment volume for an electrolyte, preferably liquid, and inside which a membrane permeable to protons is placed so as to divide the containment volume into an anodic compartment and a cathodic compartment.
- the anode is placed in the anodic compartment and at least partially immersed in the electrolyte, while the cathode is placed in the cathodic compartment and at least partially immersed in the electrolyte.
- the cathode is preferably obtained according to the above-mentioned method, such that the active surface of the copper substrate, placed in contact, during use, with said electrolyte or directly in contact with the gaseous carbon dioxide, has a nanostructured surface morphology with nanocubes having dimensions varying between 100 nm and 1000 nm and preferential crystallographic orientation according to Miller's indices (2,0,0). More precisely, the two-electrode electrochemical system described is particularly effective for the development of syngas, a fundamental precursor for the industrial synthesis of hydrocarbon fuels.
- the development of nanostructured copper cathodes according to a fine morphology with a cubic structure i.e., neutral copper nanocubes with sides varying between 100 nm and 1000 nm with crystallographic orientation (2,0,0) and with excellent catalytic properties, allows to obtain total current densities greater than 50 mA/cm 2 at an applied electric potential of -1500 mV with high carbon dioxide reduction yields even in an aqueous environment (in which the water reduction is normally kinetically preferred) using plate-type geometry electrodes.
- figure 1 illustrates, in schematic view, a flow chart representative of the process for forming and regenerating a copper cathode for an electrochemical cell
- figure 2 illustrates, with an SEM spectroscopy image, an active surface of an electrocleaned copper substrate by acidic treatment
- figure 3 illustrates, with an SEM spectroscopy image, the surface morphology of the active surface following anodisation
- figures 4a-4d illustrate, with an SEM spectroscopy image, different concentrations and dimensions of the nanocubes obtainable with the electrochemical reduction step
- figure 5 illustrates, with an AFM spectroscopy image, the nanostructured substrate surface with nanocubes
- figures 6a and 6b illustrate, with an SEM spectroscopy image, anodised “sponge"-type copper substrates
- FIG. 7 illustrates, in schematic view, an electrochemical cell
- FIG. 8 illustrates a profile of a chronoamperometry interspersed with interfacial regeneration cycles on a nanostructured copper substrate
- FIG. 9 illustrates a histogram graph representative of the faradic efficiencies for the reduction of carbon dioxide in water at pH 7.4 as a function of the electric potential applied;
- FIG. 10 illustrates a graph representative of the linear scanning voltammetry in copper sponges (those nanostructured in red; the initial, superficially non-functionalised ones in black) in the presence of saturated aqueous carbon dioxide;
- figure 11 illustrates, in schematic view, a flow chart representative of a variant embodiment of the process illustrated in figure 1 ;
- FIG. 12 illustrates, with reference to a plate-type substrate, the graph of faradic efficiency at different operating potentials
- FIG. 13 illustrates the graph representative of the comparison of the production efficiency for carbon monoxide between plate-type copper and nanostructured copper foam-type substrates
- - figures 14a, 14b illustrate, respectively with reference to a plate-type and a sponge-type substrate, the current density graphs at different operating potentials.
- the present invention relates to a process for forming and regenerating a copper cathode for an electrochemical cell and an electrochemical cell for the production of industrial products, for example syngas.
- an electrochemical cell is generically indicated with the number 10
- a process for forming and regenerating a cathode is indicated with the number 500.
- copper cathode means both a substrate made internally of copper metal and a substrate made of a material other than copper, for example carbon fibres or sponges, on which a sufficiently thick copper layer, i.e., having a minimum thickness of about 500 nanometres, has been deposited (by conventional electrochemical or physical deposition methods).
- FIG. 1 schematically illustrates a process 500 for forming and regenerating a copper cathode 1 for an electrochemical cell 10 for the production of industrial products, for example syngas.
- the process comprises the operating steps of:
- step 501 preparing a copper substrate 2 capable of defining an electrode, both during the steps of the same process and during the use of the electrochemical cell 10 (i.e., when the completed cathode 1 is installed in the electrochemical cell 10);
- step 502 anodising the substrate 2 in an electrolytic solution based on sulphates and chlorides for a period of at least 1 minute, preferably between 1 minute and 10 minutes, at an AC electric potential varying between 0 mV and +2000 mV, at a frequency varying between 100 Hz and 1500 Hz and at atmospheric pressure and ambient temperature so that copper salts form and are deposited on an active surface 3 of the substrate
- step 503 carrying out an electrochemical reduction of the anodised substrate 2 in an electrolytic working solution having a non-acidic pH so that catalytic neutral copper (Cu 0 ) nanostructures 4 form on the active surface 3 in the form of nanocubes, where different crystalline orientations can be observed, preferably towards those of the type (2,0,0), with sides varying between 100 nm and 1000 nm and a surface density varying depending on the time spent during the anodisation step.
- Cu 0 catalytic neutral copper
- the surface density of the copper nanocubes varies between 1 - 2 nanocubes per mm 2 (square micrometre) and about ten nanocubes per mm 2 associated in agglomerates and columnar structures, as can be seen in the accompanying figures (Fig. 4a-4d).
- the process can be calibrated by controlling the few simple variable parameters which occur during the carrying out thereof, i.e., the working frequency, the time interval of the surface electrochemical reactions, the electrolyte used during the steps and the electric working voltage (minimum and maximum).
- the substrate 2 prepared at the beginning of the process may be a substantially two-dimensional element, such as a plate, or a three-dimensional structure, such as a sponge or a foam advantageous for the scalability characteristic thereof.
- the cathode 1 is made through a copper plate-type substrate 2 having a degree of purity greater than 99% and a thickness of about 0.127 mm.
- functionalise structures with a different macroscopic morphology with respect to the first ones, for example copper sponges normally present on the market in various degrees of porosity and in different thicknesses (figure 6a).
- the use of such porous three-dimensional structures allows to extend the extension of the active surface 3 and potentially favours the formation of surface depressions necessary to ensure local pH variations favourable for the CO 2 reduction reactions.
- the pulsed anodic treatment effectively shows the appearance of cubically oriented nanostructures.
- the step of anodising the substrate 2 is carried out in an electrolytic aqueous solution comprising potassium sulphate (K 2 SO 4 ) at a concentration of about 0.10 M and potassium chloride (KCI) at a concentration of about 0.01 M, which is usually known as “Derived Oxide Treatment”.
- K 2 SO 4 potassium sulphate
- KCI potassium chloride
- the step of anodising the substrate 2 is carried out with the application of a slightly oxidising AC electric potential of the square wave type.
- the step of anodising the substrate 2 is carried out between 0 mV and +1500 mV, preferably between 0 mV and +1000 mV, and/or at a frequency which can vary between 100 Hz and 1500 Hz, preferably at a frequency of about 1000 Hz for a period of about 5 minutes.
- the frequency value and duration of the anodisation period can be varied to obtain similar results.
- the anodisation of the substrate 2 is carried out in a singlecompartment cell without the ion-permeable separation membrane and in the presence of a metal platinum metal counter-electrode. Even more preferably, the square wave electrolysis occurs with the combination of the aforesaid parameters so as to obtain the surface morphology of the anodised cathode 1 illustrated in figure 3.
- the substrate 2 is of the plate type, it is placed on a horizontal supporting surface so that the active surface 3 is turned upwards for the deposit of the copper salts.
- the plate-type substrate 2 is kept in a horizontal position so as to favour the permanence on the active surface 3 of the copper salts formed during the process conducted entirely in ambient atmosphere and at ambient temperature.
- the electrochemical reduction step of the substrate 2 is carried out in an electrolytic working solution comprising a buffer solution of bicarbonate (buffer solution with CO 2 ) and potassium bicarbonate (KHCOa) at a concentration of about 0.50 M.
- an electrolytic working solution comprising a buffer solution of bicarbonate (buffer solution with CO 2 ) and potassium bicarbonate (KHCOa) at a concentration of about 0.50 M.
- the electrochemical reduction step of the substrate 2 is performed in an electrolytic working solution having a pH equal to about 7.4, obtained following bubbling of carbon dioxide gas (CO 2 gas) into the same electrolytic working solution.
- the anodised substrate 2 is subjected to a first electrochemical reduction directly in the reaction cell, i.e., the electrochemical cell 10, under the electrical CO 2 reduction conditions and potentials, i.e., preferably with negative potentials varying from -200 mV to -1600 mV.
- the electrochemical reduction will be carried out with a combination of the parameters described above.
- the final morphology of the nanostructured active surface 3 will be determined by the conditions under which it was decided to perform the previous anodisation step.
- the surface density and dimensions of the nanocubes will depend on the anodisation parameters and, in particular, on the duration of the working time interval.
- the surface density of the copper nanocubes varies between 1 -2 nanocubes per mm 2 (square micrometre) and about ten nanocubes per mm 2 associated in agglomerates and columnar structures.
- figure 5 illustrates a further image of the nanostructured active surface 3 of the cathode 1 obtained by AFM spectroscopy.
- the process comprises a preliminary step of electrocleaning (step 504) the active surface 3, preferably to be carried out prior to the anodising step, in which the copper substrate 2 is immersed in an acidic electrolytic mixture at ambient temperature and with no inert atmosphere.
- the preliminary electrocleaning step provides that the acidic electrolyte mixture used preferably contains 85% phosphoric acid (H 3 PO 4 ).
- the preliminary electrocleaning step uses a titanium counter-electrode to which an electric potential of about +4000 mV is applied for a time interval of about 5 minutes.
- the active surface 3 of the substrate 2 is completely free from any particulates or molecules capable of inhibiting the deposition of copper salts for the formation of the catalytic nanostructures 4.
- the process comprises a step of cleaning (step 505) the anodised substrate 2 carried out, preferably, following the anodising step and prior to the electrolytic reduction step.
- the anodised substrate 2 is immersed in a potassium bicarbonate (KHCO 3 ) mixture having a concentration equal to about 0.50 M.
- KHCO 3 potassium bicarbonate
- a chromatic change of the treated active surface 3 is observed, which varies from a light white/yellow to a deep yellow/orange colour.
- the process comprises a preliminary step of purification (step 506) of the potassium bicarbonate mixture used for the step of cleaning the anodised substrate 2.
- the preliminary cleaning step is an electrolysis with two electrodes, preferably made of titanium, maintained at an electric potential of about -2000 mV so as to eliminate any unwanted metal species.
- the purification of the electrolyte is preferably carried out, as metal cation impurities (especially Fe(ll), Zn(ll) and Pb(ll)) may be present inside the electrolyte. These impurities can lead to the inhibition of the copper catalytic nanostructures 4, i.e., nanocubes, following their deposition on the surface of the cathode 1 .
- each electrolytic solution or mixture used during the process is preferably prepared from salts with a high degree of purity (i.e., with values usually indicated as “99+%”) and/or low-conductivity deionised water, e.g., MilliQ® water.
- the steps of the process for forming and regenerating a copper cathode for an electrochemical cell are schematically summarised below: preparing a copper substrate 2 defining an electrode; preliminary cleaning said substrate 2 by using an acidic electrolytic mixture (figure 2, figure 6a); anodising the substrate 2 in an electrolytic solution of sulphates and chlorides at atmospheric pressure and ambient temperature with an electric potential with a square wave at a predefined frequency and for a preset time interval according to the density and dimension to be obtained for the surface nanocubes (figure 3); preparing a mixture of potassium bicarbonate; electrochemically purifying said potassium bicarbonate mixture; electrochemically reducing the copper of the substrate 2 so as to definitively form the fine surface morphology comprising copper nanocubes having predefined density and dimensions (figures 4a-4d, 5, 6b).
- the surface density of the copper nanocubes varies between 1 -
- all the steps of the aforementioned process can be carried out in the same cell, changing the electrolyte and possibly the counter- electrode (anode) necessary for the specific step.
- the process can be implemented initially for forming the nanostructured copper cathode 1 and superficially functionalised with the nanocubes, and subsequently with electrolyte substitution, for the surface regeneration of the cathode 1 .
- the process comprises a surface deposit step (step 507) following the electrochemical reduction step (step 503) in which at least the active surface
- the surface deposition (or, possibly, even a partial inclusion within the copper interface of the cathode 1 ) of metal materials other than copper (even those metal materials which usually do not have particular catalytic characteristics with respect to the electrochemical carbon dioxide reduction reaction) is capable of bringing benefits to the catalysis process which develops on the active surface 3 of the substrate 2.
- the surface deposition step involves depositing one or more reduction co-catalyst elements with a density varying between 10 C/cm 2 [coulomb per square centimetre] and 60 C/cm 2 .
- the reduction co-catalyst elements may be some metal materials such as, for example, indium, tin, zinc, cadmium, gold, and silver.
- preferring one co-catalyst element over another allows an increase in selectivity with respect to carbon monoxide or other products of interest.
- the optimal copper-indium ratio is between 30 C/cm 2 and 40 C/cm 2 .
- the deposit of metal indium allows to maximise the faradic yield and selectivity (with values close to 100%) of the cathode 1 with respect to syngas.
- the deposit of the reduction co-catalyst elements may be by standard physical-chemical methods, for example electrodeposition, vacuum thermal evaporation or magnetron sputtering.
- the surface functionalisation of the cathode 1 involves preparing an acidic aqueous solution containing indium salts, for example indium nitrate or sulphate at a concentration of 0.04 M and citric acid at a concentration of 0.5 M.
- indium salts for example indium nitrate or sulphate at a concentration of 0.04 M
- citric acid at a concentration of 0.5 M.
- the electrodeposition can be conducted on a standard mono-compartment cell configured with two electrodes in which the anode is preferably made of metal indium (or, alternatively, they can also be used with other inert metals such as platinum, multi-metal oxide electrodes, or catalytic metal oxides for the development of oxygen).
- FIG. 12 An operating example illustrated in figures 12, 13, 14a, 14b, shows the results of metal indium deposition on the substrate 2. More precisely, as illustrated in figure 12, such surface functionalisation of a plate-type substrate 2 allows to increase the selectivity of the cathode 1 against carbon monoxide up to average values equal to about 70% of the total faradic efficiency (considering a voltage value equal to about -1400mV vs SCE). Similarly, as illustrated in figure 13, the surface functionalisation of a copper nanostructured sponge (foam) substrate 2 confirms that carbon monoxide is one of the main products of the reduction of carbon dioxide on the surface of the cathode 1 .
- figure 13 shows the comparison of the production efficiency for the carbon monoxide between copper substrates that are sponge-type nanostructured and functionalised with indium as co-catalyst and copper plate-type substrates which have received the same functionalisation treatment.
- the ordinate axis of graph 13 shows, at different operating potentials, the actual production of carbon monoxide expressed as the faradic efficiency multiplied by the current density.
- Figures 14a and 14b illustrate the graphs of the variation in current density as the electric voltage changes, respectively, in the case of a plate-type substrate 2 and a sponge-type substrate 2.
- the aforementioned graphs show that the sponge-type substrates allow to reach current densities greater by a factor of ten with respect to similar plate-type substrates (about 300 mA/cm 2 at -1 .4 V vs SCE with respect to a value of about 30 mA/cm 2 at -1.4 V vs SCE), thus generating greater amounts of carbon monoxide than those generated by the similar plate-type substrates, more precisely by an amount about four or six times greater.
- FIG. 7 illustrates an electrochemical cell 10 for the production of industrial products, for example syngas.
- the electrochemical cell 10 for the CO 2 reduction comprises a box-like body 11 having a containment volume V in which an electrolyte 12 is contained, preferably in liquid form.
- a membrane 13 permeable to protons is placed inside the electrochemical cell 10, for example a polytetrafluoroethylene sulphonate National® membrane, capable of dividing the containment volume V into an anodic compartment 14 and a cathodic compartment 15.
- the membrane 13 is configured to prevent the oxidation reaction of the products present in the solution, that is, in the electrolyte 12 and deriving from the redox reactions on the surfaces of the electrodes.
- An anode 16 is placed inside the anodic compartment 14 and is at least partially immersed in the electrolyte 12, while the cathode 1 is placed inside the cathodic compartment 15 and is at least partially immersed in the electrolyte 12.
- the cathode 1 used comprises a copper substrate 2 with an active surface 3, placed in contact, during use, with the electrolyte 12, having a fine morphology with a cubic structure, wherein the nanocubes have sides varying between 100 nm and 1000 nm, a variable surface density and preferably a prevailing crystallographic orientation of the type (2,0,0).
- the surface density of the copper nanocubes varies between 1 - 2 nanocubes per mm 2 (square micrometre) and about ten nanocubes per mm 2 associated in agglomerates and columnar structures.
- said cathode 1 is obtained by applying the process for forming and regenerating a copper cathode 1 for an electrochemical cell 10 described above.
- the electrochemical cell 10 preferably operates also at ambient temperature and atmospheric pressure conditions.
- the working electrolyte 12 is an aqueous solution at ambient temperature and atmospheric pressure comprising potassium bicarbonate (KHCO 3 ) at a concentration of 0.50 M conditioned to the pH of the buffer solution by bubbling CO 2 .
- KHCO 3 potassium bicarbonate
- such aqueous solution is previously subjected to an electrochemical purification.
- the conditioning of the electrolyte 12 with carbon dioxide is carried out in a volume separate from the containment volume V of the box-like body 11 , and then brought into contact with the electrodes thanks to the aid of a pump.
- the use of an external device for the carbon dioxide conditioning allows the presence of gas on the surface of the electrodes to be kept constant so as to ensure constant operating conditions over time for the electrochemical cell 10.
- the use of these devices allows the main sources of carbon dioxide to be more simply interfaced with the electrochemical cell 10, since the operating conditions of the electrochemical cell 10 substantially coincide with the operation of these sources.
- the electrochemical cell 10 could be installed directly with the outlet of incinerators or aluminium production plants or many other similar situations, since the gaseous mixture of carbon dioxide and water vapour is sufficient to act as an electrolyte for catalysis.
- the electrochemical cell 10 comprises, as anode 16, a counter-electrode functionalised with carbon nanotubes or in iridium oxide or in platinum or titanium such as to ensure the development of oxygen in the respective anodic compartment 14.
- the box-like body 11 comprises an inlet opening 18 and an extraction opening 19 for the electrolyte 12 for both the anodic compartment 14 and the cathodic compartment 15.
- the box-like body 11 further comprises a first extraction mouth 20 for extracting the oxygen produced in the anodic compartment 14 and a second extraction mouth 21 for extracting the reaction gaseous products obtained in the cathodic compartment 15.
- the box-like body 11 is hermetically sealed so as to retain the gaseous products obtained in the anodic compartment 14 and in the cathodic compartment 15.
- the electrochemical cell 10 is developed in such a way as to ensure the seal of the gases produced for storage and the chemical analyses necessary for verifying the effectiveness of the electrolysis.
- the electrochemical cell is configurable to implement the steps of the process described above in order to determine the formation of a nanostructured copper cathode 1 or to regenerate a previously used nanostructured copper cathode 1 .
- the reduction of carbon dioxide tends to have a passivating action towards the electric currents developed between the anode 16 and the cathode 1 , which decrease over time. This is attributable to the adsorption of carbonate ions on the active surface 3 of the cathode 1.
- This phenomenon is easily avoided by imposing periodic regeneration cycles of the cathode 1 itself, corresponding to the application of open-circuit electric potential for limited periods of time, as can be best seen in figure 8, which illustrates the profile of a chronoamperometry interspersed with regeneration cycles of the active surface 3 of the substrate 2.
- the electrochemical cell 10 allows to obtain carbon dioxide reduction yields which, in combination with the parallel water splitting reaction, allow to surpass 60% of the faradic efficiency thanks to the development of syngas at the optimal potential of about -1500 mV.
- the proportions of the reduction products obtained represent the optimal percentages for the composition of syngas (for the predominant synthesis of alkanes).
- the percentages of the reduction products comprise on average a percentage of carbon monoxide varying from 20% to 30%, of formic acid up to 10% and hydrogen over 60% (using the electrochemical cell 10 described above) and other minor products such as ethylene (at most 4%), methane (about 1%) and traces of many other molecules containing carbon at an oxidation state of less than four. Methane is present in minimal quantities due to the complexity of the processes of reducing carbon dioxide.
- the parallel splitting reaction of the water molecule allows the remaining electric currents to be conveyed to the production of hydrogen, which is generated in the cathodic compartment 15 of the electrochemical cell 10. Instead, the parallel production of oxygen as a consequence of the oxidative process of water occurs at the anode 16.
- a copper plate-type substrate 2 (of the type shown above), it is possible to obtain total current densities in the order of 50 mA/cm 2 at a potential of -1500 mV.
- nanostructured copper sponges e.g., according to the procedure described above
- the maximum current density values are around 200 mA/cm 2 against about 50 mA/cm 2 of the initial non-nanostructured substrates.
- the active surface 3 of the cathode 1 is functionalised with one or more co-catalyst elements reducing at least the carbon dioxide.
- some of the possible catalyst reduction elements are indium, tin, zinc, cadmium, gold and silver, which are selected based on the selectivity to be induced on the cathode 1 towards carbon monoxide or other products of interest.
- the catalyst reduction elements are deposited on at least the active surface 3 of the substrate 2 by standard physical-chemical methods, for example electrochemical reduction, vacuum thermal evaporation or magnetron sputtering.
- some of the advantages of the present invention, and in particular of the electrochemical cell 10 are related to the fact of being able to operate under mild pressure conditions (about 1 bar), at ambient temperature (about 25°C) and, in the case of plate-type substrates, the considerable mechanical resistance which allows extended operation over time (up to about 12 h) and the possibility of regenerating the active surface 3 of the cathode 1 directly in the electrochemical cell 10 of the reaction, by simply replacing the electrolyte 12 and applying the corresponding electric potential values.
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