EP4136277B1 - Copper and antimony based material and electrode for the selective conversion of carbon dioxide to carbon monoxide - Google Patents
Copper and antimony based material and electrode for the selective conversion of carbon dioxide to carbon monoxide Download PDFInfo
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- EP4136277B1 EP4136277B1 EP21724756.8A EP21724756A EP4136277B1 EP 4136277 B1 EP4136277 B1 EP 4136277B1 EP 21724756 A EP21724756 A EP 21724756A EP 4136277 B1 EP4136277 B1 EP 4136277B1
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- EP
- European Patent Office
- Prior art keywords
- antimony
- electrode
- copper
- carbon
- electrocatalyst
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- 239000000463 material Substances 0.000 title claims description 56
- 229910052787 antimony Inorganic materials 0.000 title claims description 27
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 title claims description 18
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 title description 45
- 239000001569 carbon dioxide Substances 0.000 title description 39
- 229910002092 carbon dioxide Inorganic materials 0.000 title description 39
- 239000010949 copper Substances 0.000 title description 32
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 title description 29
- 229910002091 carbon monoxide Inorganic materials 0.000 title description 29
- 229910052802 copper Inorganic materials 0.000 title description 19
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title description 11
- 238000006243 chemical reaction Methods 0.000 title description 10
- 239000000203 mixture Substances 0.000 claims description 28
- 239000010411 electrocatalyst Substances 0.000 claims description 24
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 21
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 19
- 230000009467 reduction Effects 0.000 claims description 18
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 16
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(i) oxide Chemical compound [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 claims description 15
- 239000000843 powder Substances 0.000 claims description 14
- 239000004020 conductor Substances 0.000 claims description 12
- 238000004519 manufacturing process Methods 0.000 claims description 12
- 230000008569 process Effects 0.000 claims description 12
- 229910052799 carbon Inorganic materials 0.000 claims description 11
- 239000000243 solution Substances 0.000 claims description 11
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 9
- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical compound [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 claims description 9
- 229910052751 metal Inorganic materials 0.000 claims description 9
- 239000002184 metal Substances 0.000 claims description 9
- 239000002904 solvent Substances 0.000 claims description 9
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical class [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 claims description 7
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 claims description 6
- 239000006229 carbon black Substances 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 239000007864 aqueous solution Substances 0.000 claims description 5
- FAWGZAFXDJGWBB-UHFFFAOYSA-N antimony(3+) Chemical class [Sb+3] FAWGZAFXDJGWBB-UHFFFAOYSA-N 0.000 claims description 4
- 239000002244 precipitate Substances 0.000 claims description 4
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims description 3
- QGLWBTPVKHMVHM-KTKRTIGZSA-N (z)-octadec-9-en-1-amine Chemical compound CCCCCCCC\C=C/CCCCCCCCN QGLWBTPVKHMVHM-KTKRTIGZSA-N 0.000 claims description 3
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 3
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 3
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 claims description 3
- 150000001413 amino acids Chemical class 0.000 claims description 3
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 claims description 3
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 3
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 claims description 3
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 3
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 claims description 3
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 claims description 3
- 239000002041 carbon nanotube Substances 0.000 claims description 2
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 239000004744 fabric Substances 0.000 claims description 2
- 229910021389 graphene Inorganic materials 0.000 claims description 2
- 229910002804 graphite Inorganic materials 0.000 claims description 2
- 239000010439 graphite Substances 0.000 claims description 2
- 229920000554 ionomer Polymers 0.000 claims description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical group CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims 2
- 229910002651 NO3 Inorganic materials 0.000 claims 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims 2
- 238000006722 reduction reaction Methods 0.000 description 20
- 239000000047 product Substances 0.000 description 16
- 238000004458 analytical method Methods 0.000 description 14
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 8
- BDAGIHXWWSANSR-UHFFFAOYSA-N Formic acid Chemical compound OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 7
- 238000002441 X-ray diffraction Methods 0.000 description 7
- 238000002149 energy-dispersive X-ray emission spectroscopy Methods 0.000 description 7
- 239000012071 phase Substances 0.000 description 7
- 150000001875 compounds Chemical class 0.000 description 6
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 description 6
- 235000019253 formic acid Nutrition 0.000 description 6
- 239000007789 gas Substances 0.000 description 6
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 5
- -1 Cu+ ion Chemical class 0.000 description 5
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Inorganic materials O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- 150000002739 metals Chemical class 0.000 description 5
- 239000002243 precursor Substances 0.000 description 5
- 150000003839 salts Chemical class 0.000 description 5
- 229920000557 Nafion® Polymers 0.000 description 4
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 4
- JVLRYPRBKSMEBF-UHFFFAOYSA-K diacetyloxystibanyl acetate Chemical compound [Sb+3].CC([O-])=O.CC([O-])=O.CC([O-])=O JVLRYPRBKSMEBF-UHFFFAOYSA-K 0.000 description 4
- 239000003792 electrolyte Substances 0.000 description 4
- 238000002354 inductively-coupled plasma atomic emission spectroscopy Methods 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 239000000725 suspension Substances 0.000 description 4
- YEAUATLBSVJFOY-UHFFFAOYSA-N tetraantimony hexaoxide Chemical compound O1[Sb](O2)O[Sb]3O[Sb]1O[Sb]2O3 YEAUATLBSVJFOY-UHFFFAOYSA-N 0.000 description 4
- VMQMZMRVKUZKQL-UHFFFAOYSA-N Cu+ Chemical compound [Cu+] VMQMZMRVKUZKQL-UHFFFAOYSA-N 0.000 description 3
- 239000004809 Teflon Substances 0.000 description 3
- 229920006362 Teflon® Polymers 0.000 description 3
- 229910000410 antimony oxide Inorganic materials 0.000 description 3
- 229960004424 carbon dioxide Drugs 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000010931 gold Substances 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052738 indium Inorganic materials 0.000 description 3
- VTRUBDSFZJNXHI-UHFFFAOYSA-N oxoantimony Chemical compound [Sb]=O VTRUBDSFZJNXHI-UHFFFAOYSA-N 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 229910052709 silver Inorganic materials 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 229910052718 tin Inorganic materials 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 239000005751 Copper oxide Substances 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 229910052797 bismuth Inorganic materials 0.000 description 2
- 238000005119 centrifugation Methods 0.000 description 2
- 150000001879 copper Chemical class 0.000 description 2
- 229910000431 copper oxide Inorganic materials 0.000 description 2
- 229940112669 cuprous oxide Drugs 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 230000005669 field effect Effects 0.000 description 2
- 239000010408 film Substances 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 230000005855 radiation Effects 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 230000006641 stabilisation Effects 0.000 description 2
- 238000011105 stabilization Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 230000009466 transformation Effects 0.000 description 2
- 229910009112 xH2O Inorganic materials 0.000 description 2
- 239000011701 zinc Substances 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
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- 229910000881 Cu alloy Inorganic materials 0.000 description 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 238000001069 Raman spectroscopy Methods 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 229910021607 Silver chloride Inorganic materials 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 1
- TXTQARDVRPFFHL-UHFFFAOYSA-N [Sb].[H][H] Chemical compound [Sb].[H][H] TXTQARDVRPFFHL-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 150000001242 acetic acid derivatives Chemical class 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- GHPGOEFPKIHBNM-UHFFFAOYSA-N antimony(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Sb+3].[Sb+3] GHPGOEFPKIHBNM-UHFFFAOYSA-N 0.000 description 1
- QZPSXPBJTPJTSZ-UHFFFAOYSA-N aqua regia Chemical compound Cl.O[N+]([O-])=O QZPSXPBJTPJTSZ-UHFFFAOYSA-N 0.000 description 1
- 239000012736 aqueous medium Substances 0.000 description 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 238000004177 carbon cycle Methods 0.000 description 1
- 235000011089 carbon dioxide Nutrition 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- 229920001940 conductive polymer Polymers 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- NWFNSTOSIVLCJA-UHFFFAOYSA-L copper;diacetate;hydrate Chemical compound O.[Cu+2].CC([O-])=O.CC([O-])=O NWFNSTOSIVLCJA-UHFFFAOYSA-L 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000004205 dimethyl polysiloxane Substances 0.000 description 1
- 238000002848 electrochemical method Methods 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 125000003827 glycol group Chemical group 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 1
- 239000003014 ion exchange membrane Substances 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 230000002045 lasting effect Effects 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000012263 liquid product Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000002114 nanocomposite Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000003071 parasitic effect Effects 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 239000011736 potassium bicarbonate Substances 0.000 description 1
- 229910000028 potassium bicarbonate Inorganic materials 0.000 description 1
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000011946 reduction process Methods 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 238000004626 scanning electron microscopy Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000010944 silver (metal) Substances 0.000 description 1
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- 239000012798 spherical particle Substances 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- JBQYATWDVHIOAR-UHFFFAOYSA-N tellanylidenegermanium Chemical compound [Te]=[Ge] JBQYATWDVHIOAR-UHFFFAOYSA-N 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Images
Classifications
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—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
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/02—Electrodes; Manufacture thereof not otherwise provided for characterised by shape or form
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/23—Carbon monoxide or syngas
-
- 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
- C25B11/037—Electrodes made of particles
-
- 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
- C25B11/042—Electrodes formed of a single material
- C25B11/043—Carbon, e.g. diamond or graphene
-
- 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
- C25B11/061—Metal or alloy
-
- 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
Definitions
- the present invention relates to a copper and antimony based material, and an electrode obtained from this material, useful for the electrochemical reduction of carbon dioxide to carbon monoxide with high efficiency and selectivity.
- the result of the process is usually a mixture of products, which is difficult or not easy to use industrially.
- the parasitic reaction of hydrogen evolution usually occurs in higher yield than the reduction of CO 2 in aqueous electrolyte.
- electrode materials are required that can provide high CO 2 conversion efficiency and at the same time high selectivity towards a specific reaction product, in particular towards CO; materials of this kind are generally known in electrochemistry as electrocatalysts.
- gold (Au), silver (Ag) and palladium (Pd) are considered the best metal electrocatalysts to convert CO 2 into CO; however, these metals cannot be used on an industrial scale for this purpose due to their high cost and low availability.
- Patent application US 2019/0127866 A1 describes an electrocatalyst material for converting CO 2 to ethanol, comprising nanoparticles of copper or alloys thereof supported by nanometer-sized tips ("nanospikes") of carbon doped with nitrogen, boron or phosphorus.
- Copper alloys indicated as useful by this document are all those of the element with one or more elements selected from those in the Groups 3-15 of the periodic table. Alloys indicated as preferred are those between copper and an element selected from Ni, Co, Zn, In, Ag and Sn.
- the electrocatalysts of this document exhibit higher selectivity for CO 2 electroreduction than H 2 evolution with high faradic efficiency in ethanol production, with a yield in this compound of at least 60% of the mixture; other species, such as carbon monoxide, are thus produced with yields not exceeding 40%.
- the preparation of the doped carbon nanospikes makes the process not straightforward.
- the materials in this paper are produced by dissolving soluble Cu(II) and Sb(III) salts in a suspension of carbon black in ethanol, adding a base (KOH) to the suspension and allowing the system to react for 6 hours at a temperature of 80 °C obtained with an oil bath; the precipitate obtained is then washed with water and ethanol and finally dried. The mixture of powders thus obtained is then distributed on a carbon paper obtaining electrodes.
- the object of the present invention is to overcome the problems of the prior art, and in particular to provide an electrocatalyst material which allows to obtain in the electrochemical reduction reaction of CO 2 a CO yield and a selectivity towards this compound higher than with the electrocatalysts of the prior art.
- Another object of the invention is to make available a cost-effective process for large-scale production of this electrocatalyst.
- an electrocatalyst material comprising copper(I) oxide (Cu 2 O) containing antimony, wherein the amount of antimony is between 5% to 30% by weight.
- This material is used in a finely divided form to produce electrodes for the electrochemical reduction of CO 2 , wherein said material is combined with an electroconductive material.
- the invention relates to a process for the production of the electrocatalyst material, comprising the following steps:
- the inventors have found that copper(I) oxide (Cu 2 O, cuprous oxide) containing antimony in an amount between 5 and 30% by weight, when used to produce an electrode, enables the electrochemical reduction of CO 2 to CO to be achieved with higher values of faradic efficiency and selectivity than known materials.
- the compounds of the invention enable these results to be obtained by employing copper and antimony, which are inexpensive and widely available components.
- the materials of the invention will generally be referred to in the following by the notation CuzO/Sb, regardless of the specific composition.
- the Cu 2 O/Sb materials of the invention have a Sb content between 5 and 30% by weight; preferred are the materials having a Sb content between 17.2 and 23.9% by weight.
- Fig. 1 shows images obtained by field effect scanning electron microscope (FESEM) of samples of the invention with increasing Sb content ( Figs. 1(b) to 1(i) ) and, for comparison, of three samples produced following the same method as the samples of the invention but containing only copper ( Fig. 1(a) ), only antimony ( Fig. 1(k) ), and a sample not of the invention containing an amount of antimony of 36% ( Fig.
- FESEM field effect scanning electron microscope
- the weight percentage amount of Sb in the samples of the invention prepared as described in Example 1, determined by chemical analysis, is as follows: - Fig. 1(b) : 5.2; - Fig. 1(c) : 9.4; - Fig. 1(d) : 13.6; - Fig. 1(e) : 17.2; - Fig. 1(f) : 20.1; - Fig. 1(g) : 23.9; - Fig. 1(h) : 25.2 - Fig. 1(i) : 26.4.
- the materials of the invention with a Sb content of up to 26.4% by weight have a similar morphology to one another, and comprise powders in the form of essentially spherical particles with very narrow size distribution (all particles have a size of about 5 ⁇ m), composed of tightly packed nanoparticles.
- Sb-rich particles and the formation of an isolated phase consisting of crystalline Sb 2 O 3 are observed (octahedral particles in Fig. 1(j) , to be compared with the image of pure antimony oxide in Fig. 1(k) ).
- Energy dispersive X-ray spectroscopy (EDX) analysis indicates that Sb is uniformly distributed in the samples of the invention.
- XRD analysis confirms that the material is essentially copper oxide.
- Fig. 2 are shown, from top to bottom, the diffractograms for the sample containing only copper (diffractogram indicated with (Cu)), of the samples of the invention with increasing concentration of antimony (diffractograms from A to H), and of the sample containing 36% by weight of antimony (diffractogram indicated with (NI), which stands for "not of the invention”), respectively.
- FIG. 3 shows the typical spectra of the sample containing 17.2% by weight of Sb. From the XPS measurement ( Fig. 3a ) it appears that antimony is present in the sample in the form of Sb 3+ ions, as highlighted by the intense peaks relative to Sb 3d 5/2 and Sb 3d 3/2 centred at 530.06 eV and 539.45 eV, respectively.
- Fig. 3b shows instead the region of the XPS spectrum corresponding to the Cu 2p doublet; since the Cu 2p peak is difficult to deconvolve due to the overlap of numerous peaks, the Auger CuLMM region is also acquired (inset in Figure 3b ).
- the kinetic energy of the peak is 916.8 eV, which corresponds to Cu + .
- the modified Auger parameter is about 1848.8 eV, which correlates with an average oxidation state of Cu(I). It is therefore evident that copper is present in the samples in the form of Cu + ion.
- the electrocatalyst materials of the invention are poor electrical conductors per se, they are used in combination with conductive materials for the production of electrodes for CO 2 reduction.
- the conductive material is in turn in the form of powders or other finely divided form.
- a carbon-based material is generally used for this purpose, thanks to its low catalytic activity, for example carbon black, graphite, graphene, carbon nanotubes or mixtures thereof; the preferred conductive material is carbon black.
- the electrocatalyst material of the invention and the conductive material are used in weight ratios between 9:1 and 19:1.
- the mixture between the electrocatalyst material of the invention and the conductive material is distributed on a support, which may in turn be conductive or non-conductive.
- Examples of preferred supports are conductive carbon paper, conductive carbon cloth and metal mesh. Stabilization of the powder mixture on the support can be achieved with ionomers, i.e., ion conductive polymers, which form a containing and conductive film on the powders.
- ionomers i.e., ion conductive polymers
- the invention relates to a process for the production of the electrocatalyst material, which consists of steps a) to c) above.
- Step a) consists in dissolving a copper(II) salt and an antimony(III) salt in a solvent selected from ethanol, ethylene glycol, acetylacetone, diethylamine, ethylenediamine, oleylamine, N,N-dimethylformamide, mixtures of these solvents with each other, with water or with aqueous solutions of D-glucose, hydrazine hydrate, amino acids and sodium carboxymethylcellulose.
- a solvent selected from ethanol, ethylene glycol, acetylacetone, diethylamine, ethylenediamine, oleylamine, N,N-dimethylformamide, mixtures of these solvents with each other, with water or with aqueous solutions of D-glucose, hydrazine hydrate, amino acids and sodium carboxymethylcellulose.
- the most suitable salts for the purposes of the invention are acetates, sulfates and nitrates of both metals.
- the starting salts are weighed to obtain the desired weight ratio of Cu:Sb, and thus the desired weight ratio of CuzO to Sb; the calculations necessary to determine the quantities to be used of the starting salts, given a desired final composition, are of simple executability for the average chemist.
- the solution thus formed is heated in a microwave oven, within a sealed container of suitable material (e.g., Teflon) at a temperature between 180 and 230 °C for a time between 1 and 10 minutes.
- suitable material e.g., Teflon
- microwave heating in the presence of the aforementioned solvents results in the reduction of the Cu 2+ ion of the starting copper salt to Cu + ion present in the Cu 2 O oxide.
- ethylene glycol glycol functions as both a solvent and a reducing agent, and increasing temperature can increase its reducing capacity. Normally a temperature between 180 °C and 230 °C is suitable for the formation of Cu + from Cu 2+ in the given solution.
- the precipitate formed in the microwave heating is separated from the liquid phase, e.g., by filtration or centrifugation, washed with ethanol, and dried, e.g., by treatment in an oven at a temperature between 50 and 100 °C under vacuum or in an inert atmosphere.
- the process of the invention differs from that of the article by Li et al. cited above in that microwave heating is used instead of conventional heating, that as said results in the reduction of the Cu 2+ ion of the starting copper salt and the formation of the Cu 2 O phase.
- Electron microscope images and energy dispersive X-ray spectroscopy (EDX) analyses were obtained with a FESEM Supra 40 (Zeiss) equipped with a detector (Oxford Instruments Si(Li)) for energy dispersive X-ray spectroscopy (EDX) analyses.
- XRD diffractograms were recorded in the 2 ⁇ 25-80° range with a step (20) of 0.017° and a counting time of 0.45 seconds.
- This example relates to the synthesis of the materials of the invention.
- the last column of the table shows the values of Sb content in each of the samples of the invention, obtained by ICP-OES analysis (the data for the Cu and Sb samples are not shown because naturally in these two cases the analysis for the determination of the percentage content of Sb was not carried out).
- Table 1 Sample Amount of precursor (mg) Sb content (% by weight) Cu(OAc) 2 ⁇ xH 2 O Sb(OAc) 3 Cu 900 0 / A 900 164 5.2 B 900 246 9.4 C 900 295 13.6 D 900 328 17.2 E 900 410 20.1 F 900 470 23.9 G 900 492 25.2 H 900 600 26.4 NI 900 820 36.0 Sb 0 900 /
- the indicated amounts of precursors were dissolved in 40 ml of ethylene glycol and 5 ml of double distilled H 2 O (resistivity about 18 M ⁇ •cm). Each solution was then transferred to a Teflon container (volume 100 mL). The Teflon container was sealed, placed in a microwave oven (Milestone, STARTSynth, HPR-1000-10S segment with temperature and pressure control), heated to 220 °C and then maintained at this temperature by powering the oven with a maximum power of 900 W for a total irradiation time of 2 minutes. After cooling to room temperature, the suspended product in each container was separated by centrifugation and washed twice with double-distilled H 2 O and subsequently once with ethanol. Each powder sample was finally dried under vacuum at 60 °C overnight.
- the samples of the invention were examined by scanning electron microscopy and EDX analysis to determine the morphology (also for Cu and Sb samples) and the antimony distribution, by X-ray diffraction to determine the crystal structure (also for Cu and Sb samples) and by XPS to determine the oxidation state of Cu and Sb; the results of the three analyses have been discussed above with reference to Figures 1 , 2 and 3 respectively.
- This example relates to the production of electrodes for electrochemical CO 2 reduction using the materials of the invention (samples A-H) and the three comparison materials (samples Cu, Sb and NI).
- Each electrode was prepared by mixing 10 mg of sample A-H, Cu, Sb or NI, 1 mg of carbon black from acetylene, 90 ⁇ l of Nafion ® 117 solution and 320 ⁇ l of isopropanol. Each mixture was sonicated for 30 minutes until a uniform suspension was obtained. Each suspension was then used to coat a carbon paper covered with a gas permeable layer (GDL; SIGRACET 28BC, SGL Technologies); the geometric area of each electrode was 1.5 cm 2 . The obtained electrode was dried at 60 °C overnight to evaporate the solvents. The electrocatalyst loading on each electrode was approximately 3.0 mg cm -2 .
- the electrodes thus obtained are referred to in the following by the abbreviations E x , where the subscript x corresponds to the sample A-H, Cu, Sb or NI used for its production.
- This example refers to the measurement of the CO 2 reduction efficiency of the electrodes prepared in the previous Example.
- Electrochemical measurements were performed with a cell having the configuration schematically shown in Fig. 4 ; the cell as a whole, 10, is shown in the figure enclosed by a discontinuous line.
- the cell has two compartments separated by an ion exchange membrane 11 (Nafion ® N117 membrane, Sigma-Aldrich), and adopts a three-electrode configuration. Each compartment has a total volume of 10 ml and contains 7 ml of electrolyte, and thus 3 ml of headspace.
- the reference electrode, 12, is an Ag/AgCl electrode (1 mm, lossless LF-1) that is inserted into the cathode compartment.
- the counter electrode, 13, is a Pt foil (Goodfellow, 99.95%).
- the working electrode i.e., the electrode of the invention
- element 14 An aqueous solution of 0.1 M KHCO 3 was used as the electrolyte solution.
- gaseous CO 2 is fed into both half-cells from the lower part of the two compartments, while the mixture of products on which the results are evaluated is extracted from the cathode compartment (on the right in the figure); most of this mixture is sent to the separation and purification stage (performed with methods known in the field and not described in this text), while a fraction of the mixture is sent to the analysis.
- Chronoamperometric measurements were performed using a CHI760D electrochemical workstation (CH Instruments, Inc., USA).
- FE faradic efficiency
- the E Sb electrode does not produce CO at either test potential.
- the Cu electrode has poor selectivity for CO, with FE CO values below 10%.
- the comparison E NI electrode shows poor selectivity values towards CO, probably because it is formed by a mixture containing only a small amount of active material together with a completely inactive material (antimony oxide).
- the E A -E H electrodes of the invention exhibit high selectivity towards CO, with FEco above 80% for all A-H materials at -0.79 V.
- D and E show excellent selectivity values for CO, of at least 90% at both potentials.
- This example relates to the measurement of CO 2 reduction with an electrode of the invention at various potentials.
- the E D electrode which gave the best results in Example 3, was tested at five different potential values ranging from -0.69 V to -1.09 V. In each test, the evolution of CO and H 2 over time was evaluated during tests lasting between one and two hours.
- Figures 5(a) to 5(e) report tests performed at the following potentials: 5(a) -0.69 V; 5(b) -0.79 V; 5(c) -0.89 V; 5(d) -0.99 V; 5(e) -1.09 V.
- the tests at -0.79 V and -0.99 V are the same as those whose results have already been reported in the previous example.
- the results of these tests are provided in summary form in the graph in Fig. 5(f) , in which the faradic efficiency values for CO and H 2 , taken when the reduction process has reached steady state, are reported at all evaluated potentials.
- FE H2 values remain low ( ⁇ 9%) from -0.69 V to -1.09 V. No other gas phase products other than CO and H 2 were detected. Liquid products (e.g., HCOOH) were not quantified, but can be assumed to be present in very small or negligible amounts, since the total faradic efficiency for CO and H 2 measured in all tests is around 100%.
- Liquid products e.g., HCOOH
- the electrocatalyst materials of the invention catalyze the electrochemical reduction of CO 2 with high selectivity toward CO.
- the materials of the invention then offer further advantages.
- antimony and copper, and the compounds thereof used as precursors in the process of the invention are inexpensive materials; moreover, the production of these materials is simple and easily scalable at an industrial level, also because it does not employ toxic or harmful products; the invention therefore offers a technically viable and competitive alternative to the use of metals such as Au, Ag and Pd.
- the materials of the invention are in powder form, they can be used in reactors with various configurations as a gas diffusion electrode (GDE) and different sizes.
- GDE gas diffusion electrode
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Description
- The present invention relates to a copper and antimony based material, and an electrode obtained from this material, useful for the electrochemical reduction of carbon dioxide to carbon monoxide with high efficiency and selectivity.
- Massive emissions of carbon dioxide (CO2), also known as carbonic anhydride, due to the burning of fossil fuels, have been recognized as responsible for global climate change. To tackle this problem, strategies such as CO2 capture and storage are being studied, with the aim of slowing or even stopping the accumulation of CO2 in the atmosphere. The transformation of captured CO2 into additional chemicals, fuels or other products is of paramount importance to achieve a sustainable carbon cycle and to store energy in the long term. Among the different technologies for CO2 transformation, electrochemical conversion is considered particularly interesting since it can use energy obtained from renewable sources. This technology, although very promising, is of non-immediate applicability due to the high stability of the CO2 molecule, the slow kinetics and the complex mechanisms of the CO2 reduction reaction.
- CO2 reduction can occur according to several proton-coupled electron transfer processes. CO2 reduction reactions for the production of compounds containing a single carbon atom and the electrochemical evolution of H2 are reported below as R1-R5, together with their standard potentials:
CO2 + 2 H+ + 2 e- → CO + H2O E0 = -0.11 V (R1) COz + 2 H+ + 2 e- → HCOOH E0 = - 0.25 V (R2) CO2 + 8 H+ + 8 e- → CH4 + 2 H2O E0 = + 0.17 V (R3) CO2 + 6 H+ + 6 e- → CH3OH + H2O E0 = + 0.02 V (R4) 2 H+ + 2 e- → H2 E0 = 0 V (R5) - Values of E0 are reported under standard conditions (1 atm and 25 °C) with respect to the reversible hydrogen electrode (RHE) in aqueous media. Unless otherwise stated, all potentials in this description refer to the RHE.
- Among the numerous products of CO2 reduction, formic acid (HCOOH) and carbon monoxide (CO) are the only economically viable products that have been obtained so far with relevant productivity. CO is highly desired in the industrial sector, since its mixture with hydrogen (H2), i.e., synthetic gas or syngas, can be converted into hydrocarbons through the Fischer-Tropsch process.
- Since, however, the values of the standard potentials of the above reactions are similar, the result of the process is usually a mixture of products, which is difficult or not easy to use industrially. In addition, the parasitic reaction of hydrogen evolution usually occurs in higher yield than the reduction of CO2 in aqueous electrolyte.
- Therefore, electrode materials are required that can provide high CO2 conversion efficiency and at the same time high selectivity towards a specific reaction product, in particular towards CO; materials of this kind are generally known in electrochemistry as electrocatalysts.
- According to experimental and theoretical studies, gold (Au), silver (Ag) and palladium (Pd) are considered the best metal electrocatalysts to convert CO2 into CO; however, these metals cannot be used on an industrial scale for this purpose due to their high cost and low availability.
- In addition to the previous materials, the electrocatalytic properties, in CO2 reduction, of metals such as copper (Cu), zinc (Zn), tin (Sn), indium (In) and bismuth (Bi) have been studied. Cu alone has no good selectivity for any product; Zn has sufficient, but not optimal, selectivity for CO production; Sn, In and Bi are selective for HCOOH production.
- In some papers, the properties as electrocatalysts of compositions other than single metals are discussed.
- Patent application
US 2019/0127866 A1 describes an electrocatalyst material for converting CO2 to ethanol, comprising nanoparticles of copper or alloys thereof supported by nanometer-sized tips ("nanospikes") of carbon doped with nitrogen, boron or phosphorus. Copper alloys indicated as useful by this document are all those of the element with one or more elements selected from those in the Groups 3-15 of the periodic table. Alloys indicated as preferred are those between copper and an element selected from Ni, Co, Zn, In, Ag and Sn. The electrocatalysts of this document exhibit higher selectivity for CO2 electroreduction than H2 evolution with high faradic efficiency in ethanol production, with a yield in this compound of at least 60% of the mixture; other species, such as carbon monoxide, are thus produced with yields not exceeding 40%. In addition to the fact that a mixture of products is produced, the preparation of the doped carbon nanospikes makes the process not straightforward. - The article "Achieving highly selective electrocatalytic CO2 reduction by tuning CuO-Sb2O3 nanocomposites", Y. Li et al., ACS Sustainable Chem. Eng. 2020, 8, 12, 4948-4954, describes an electrocatalyst material comprising a mixture of carbon in a finely divided form ("carbon black") and powders of a mixed oxide of copper(II) (CuO) and antimony(III) (Sb2O3). The purpose of this study is to identify the best conditions for converting CO2 to CO. The materials in this paper are produced by dissolving soluble Cu(II) and Sb(III) salts in a suspension of carbon black in ethanol, adding a base (KOH) to the suspension and allowing the system to react for 6 hours at a temperature of 80 °C obtained with an oil bath; the precipitate obtained is then washed with water and ethanol and finally dried. The mixture of powders thus obtained is then distributed on a carbon paper obtaining electrodes. In the section "Results and discussion" of the article, it is confirmed that copper oxide is in the form of CuO (i.e., copper is in oxidation state (II)) and that antimony oxide is in the form of Sb2O3 (i.e., antimony is in oxidation state (III)), by X-ray diffraction analysis (XRD,
Fig. 1 .a of the article) showing the presence of the characteristic peaks of CuO and Sb2O3, by X-ray photoelectron spectroscopy (XPS,Fig. 1 .b) and by Raman spectroscopy (Fig. 1 .c). As shown in the article (seeFigure 3 .b), the best results are obtained with the molar ratio Cu:Sb 10: 1, with which faradic yields of approximately 10% for HCOOH, 10% for H2 and 80% for CO are obtained, while the authors report that as the Sb content increases, the CO yield drops rapidly. The results obtained with the best material of this article are already interesting, but still not optimal both as CO yield and as selectivity towards this compound (a mixture of three products is obtained). - The object of the present invention is to overcome the problems of the prior art, and in particular to provide an electrocatalyst material which allows to obtain in the electrochemical reduction reaction of CO2 a CO yield and a selectivity towards this compound higher than with the electrocatalysts of the prior art. Another object of the invention is to make available a cost-effective process for large-scale production of this electrocatalyst.
- These objects are achieved with the present invention, which in a first aspect relates to an electrocatalyst material comprising copper(I) oxide (Cu2O) containing antimony, wherein the amount of antimony is between 5% to 30% by weight.
- This material is used in a finely divided form to produce electrodes for the electrochemical reduction of CO2, wherein said material is combined with an electroconductive material.
- In a second aspect thereof, the invention relates to a process for the production of the electrocatalyst material, comprising the following steps:
- a) dissolving a copper(II) salt and an antimony(III) salt in a solvent selected from ethanol, ethylene glycol, acetylacetone, diethylamine, ethylenediamine, oleylamine, N,N-dimethylformamide, mixtures of these solvents with each other, with water or with aqueous solutions of D-glucose, hydrazine hydrate, amino acids or sodium carboxymethylcellulose, obtaining a solution;
- b) heating the solution in a microwave oven at a temperature between 180 and 230 °C for a time between 1 and 10 minutes;
- c) separating the precipitate from the solution and its drying.
- The invention will be described in detail in the following with reference to the figures, in which:
-
Fig. 1 shows photomicrographs obtained by field effect scanning electron microscope (FESEM) of various materials of the invention and three comparison materials; -
Fig. 2 shows results of X-ray diffraction (XRD) of powder samples of materials of the invention having different compositions and three comparison materials; -
Fig. 3 shows spectra obtained by X-ray photoelectron spectroscopy (XPS) for Cu and Sb on a sample of the invention; -
Fig. 4 represents in a schematic form an electrolytic cell used to carry out the CO2 reduction tests reported in the Examples section; -
Fig. 5 shows graphs representative of the faradic efficiency in the conversion of CO2 to CO obtained with a material of the invention. - The inventors have found that copper(I) oxide (Cu2O, cuprous oxide) containing antimony in an amount between 5 and 30% by weight, when used to produce an electrode, enables the electrochemical reduction of CO2 to CO to be achieved with higher values of faradic efficiency and selectivity than known materials. The compounds of the invention enable these results to be obtained by employing copper and antimony, which are inexpensive and widely available components.
- A material similar to that of the present invention has been described in the paper "Optimal synthesis of antimony-doped cuprous oxides for photoelectrochemical applications", Dae Yun et al., Thin Solid Films 671 (2019) 120-126. However, this paper is directed to the study of the influence of Sb concentration on the structural, electrical and photoelectrochemical properties of cuprous oxide thin films for the purpose of photoelectrochemical water splitting; besides, this study reports materials in which the amount of Sb reaches at most up to 1% in moles, and indicates as a preferred material for the mentioned purpose CuzO doped with 0.75% molar Sb.
- The materials of the invention will generally be referred to in the following by the notation CuzO/Sb, regardless of the specific composition.
- The Cu2O/Sb materials of the invention have a Sb content between 5 and 30% by weight; preferred are the materials having a Sb content between 17.2 and 23.9% by weight.
- The materials of the invention are obtained and used in powder form. The morphology of these powders is uniform and homogeneous at least up to the Sb concentration of 26.4%.
Fig. 1 shows images obtained by field effect scanning electron microscope (FESEM) of samples of the invention with increasing Sb content (Figs. 1(b) to 1(i) ) and, for comparison, of three samples produced following the same method as the samples of the invention but containing only copper (Fig. 1(a) ), only antimony (Fig. 1(k) ), and a sample not of the invention containing an amount of antimony of 36% (Fig. 1(j) ); in particular, the weight percentage amount of Sb in the samples of the invention prepared as described in Example 1, determined by chemical analysis, is as follows:- Fig. 1(b) :5.2; - Fig. 1(c) :9.4; - Fig. 1(d) :13.6; - Fig. 1(e) :17.2; - Fig. 1(f) :20.1; - Fig. 1(g) :23.9; - Fig. 1(h) :25.2 - Fig. 1(i) :26.4. - As can be seen in the images, the materials of the invention with a Sb content of up to 26.4% by weight have a similar morphology to one another, and comprise powders in the form of essentially spherical particles with very narrow size distribution (all particles have a size of about 5 µm), composed of tightly packed nanoparticles. For concentrations higher than 26.4%, Sb-rich particles and the formation of an isolated phase consisting of crystalline Sb2O3 are observed (octahedral particles in
Fig. 1(j) , to be compared with the image of pure antimony oxide inFig. 1(k) ). Energy dispersive X-ray spectroscopy (EDX) analysis indicates that Sb is uniformly distributed in the samples of the invention. - XRD analysis confirms that the material is essentially copper oxide. In
Fig. 2 are shown, from top to bottom, the diffractograms for the sample containing only copper (diffractogram indicated with (Cu)), of the samples of the invention with increasing concentration of antimony (diffractograms from A to H), and of the sample containing 36% by weight of antimony (diffractogram indicated with (NI), which stands for "not of the invention"), respectively. As can be seen in the figure, in the samples of the invention up to a Sb content of 26.4% by weight, only peaks attributable to the Cu2O phase are present (with decreasing intensity as the Sb content increases); in the sample with a Sb content of 36.0% by weight, peaks attributable to the Sb2O3 phase appear instead, although with low intensity. - The composition is also confirmed by high-resolution (HR) XPS spectroscopy.
Figure 3 shows the typical spectra of the sample containing 17.2% by weight of Sb. From the XPS measurement (Fig. 3a ) it appears that antimony is present in the sample in the form of Sb3+ ions, as highlighted by the intense peaks relative toSb 3d5/2 andSb 3d3/2 centred at 530.06 eV and 539.45 eV, respectively.Fig. 3b shows instead the region of the XPS spectrum corresponding to theCu 2p doublet; since theCu 2p peak is difficult to deconvolve due to the overlap of numerous peaks, the Auger CuLMM region is also acquired (inset inFigure 3b ). The kinetic energy of the peak is 916.8 eV, which corresponds to Cu+. The modified Auger parameter is about 1848.8 eV, which correlates with an average oxidation state of Cu(I). It is therefore evident that copper is present in the samples in the form of Cu+ ion. - Since the electrocatalyst materials of the invention are poor electrical conductors per se, they are used in combination with conductive materials for the production of electrodes for CO2 reduction. Preferably, the conductive material is in turn in the form of powders or other finely divided form. A carbon-based material is generally used for this purpose, thanks to its low catalytic activity, for example carbon black, graphite, graphene, carbon nanotubes or mixtures thereof; the preferred conductive material is carbon black. The electrocatalyst material of the invention and the conductive material are used in weight ratios between 9:1 and 19:1. For the production of the electrode, the mixture between the electrocatalyst material of the invention and the conductive material is distributed on a support, which may in turn be conductive or non-conductive. Examples of preferred supports are conductive carbon paper, conductive carbon cloth and metal mesh. Stabilization of the powder mixture on the support can be achieved with ionomers, i.e., ion conductive polymers, which form a containing and conductive film on the powders.
- In a second aspect thereof, the invention relates to a process for the production of the electrocatalyst material, which consists of steps a) to c) above.
- Step a) consists in dissolving a copper(II) salt and an antimony(III) salt in a solvent selected from ethanol, ethylene glycol, acetylacetone, diethylamine, ethylenediamine, oleylamine, N,N-dimethylformamide, mixtures of these solvents with each other, with water or with aqueous solutions of D-glucose, hydrazine hydrate, amino acids and sodium carboxymethylcellulose. The most suitable salts for the purposes of the invention are acetates, sulfates and nitrates of both metals. The starting salts are weighed to obtain the desired weight ratio of Cu:Sb, and thus the desired weight ratio of CuzO to Sb; the calculations necessary to determine the quantities to be used of the starting salts, given a desired final composition, are of simple executability for the average chemist.
- The solution thus formed is heated in a microwave oven, within a sealed container of suitable material (e.g., Teflon) at a temperature between 180 and 230 °C for a time between 1 and 10 minutes. In addition to causing the metal salts to react to form the final material, microwave heating in the presence of the aforementioned solvents results in the reduction of the Cu2+ ion of the starting copper salt to Cu+ ion present in the Cu2O oxide. In the case of ethylene glycol, glycol functions as both a solvent and a reducing agent, and increasing temperature can increase its reducing capacity. Normally a temperature between 180 °C and 230 °C is suitable for the formation of Cu+ from Cu2+ in the given solution.
- Finally, the precipitate formed in the microwave heating is separated from the liquid phase, e.g., by filtration or centrifugation, washed with ethanol, and dried, e.g., by treatment in an oven at a temperature between 50 and 100 °C under vacuum or in an inert atmosphere.
- The process of the invention differs from that of the article by Li et al. cited above in that microwave heating is used instead of conventional heating, that as said results in the reduction of the Cu2+ ion of the starting copper salt and the formation of the Cu2O phase.
- The invention will be further described in the experimental section below.
- The following precursors were used in the preparation of the samples:
- copper(II) acetate, Cu(OAc)2·xH2O (Sigma-Aldrich, catalogue No. 66923-66-8 degree of hydration, ~1), 98% purity;
- antimony(III) acetate, Sb(OAc)3, (Sigma-Aldrich, catalogue No. 6923-52-0), 99.99% purity;
- ethylene glycol (Sigma-Aldrich, catalogue No. 107-21-1), 99.8% purity;
- Nafion® 117 solution (Sigma-Aldrich, catalogue no. 31175-20-9; Nafion is a registered trademark of E. I. du Pont de Nemours and Company), purity: ~ 5% in a mixture of lower aliphatic alcohols and water.
- Chemical composition analyses of the samples were performed by inductively coupled plasma optical emission spectroscopy (ICP-OES, iCAP 7600 DUO instrument, Thermo Fisher Scientific); each analysis was performed by dissolving 5.0 mg of the sample in 10.0 ml of an aqueous solution with 10% aqua regia.
- Electron microscope images and energy dispersive X-ray spectroscopy (EDX) analyses were obtained with a FESEM Supra 40 (Zeiss) equipped with a detector (Oxford Instruments Si(Li)) for energy dispersive X-ray spectroscopy (EDX) analyses.
- The phase composition of each sample was determined by X-ray diffraction (XRD) with a diffractometer (PANalytical X'Pert Pro equipped with an X'Celerator detector) that uses Cu Kα radiation (λ = 1.54178 Å) generated at 40 kV and 30 mA. XRD diffractograms were recorded in the 2θ 25-80° range with a step (20) of 0.017° and a counting time of 0.45 seconds.
- High-resolution (HR) XPS analyses were performed with a PHI 5000 VersaProbe instrument (Physical Electronics) using monochromatic Al Kα (1486.6 eV) radiation.
- Analyses of gaseous products derived from CO2 electroreduction were performed in real time with an INFICON Fusion® microgascromatograph (µGC) equipped with two channels with a 10 m Rt-Molsieve 5A column and an 8 m Rt-Q-Bond column, respectively, and thermal conductivity microdetectors (micro-TCD).
- This example relates to the synthesis of the materials of the invention.
- Seven samples of materials of the invention with different Sb contents were prepared using copper acetate and antimony acetate as precursors, used in the amounts shown in Table 1. The samples of the invention are indicated as A-H. For comparison, a sample from copper acetate alone (sample referred to as "Cu" in the table), a sample from antimony acetate alone (sample "Sb"), and a sample of mixed Cu/Sb composition not of the invention (sample "NI") were also produced in the identical manner described below. The last column of the table shows the values of Sb content in each of the samples of the invention, obtained by ICP-OES analysis (the data for the Cu and Sb samples are not shown because naturally in these two cases the analysis for the determination of the percentage content of Sb was not carried out).
Table 1 Sample Amount of precursor (mg) Sb content (% by weight) Cu(OAc)2·xH2O Sb(OAc)3 Cu 900 0 / A 900 164 5.2 B 900 246 9.4 C 900 295 13.6 D 900 328 17.2 E 900 410 20.1 F 900 470 23.9 G 900 492 25.2 H 900 600 26.4 NI 900 820 36.0 Sb 0 900 / - The indicated amounts of precursors were dissolved in 40 ml of ethylene glycol and 5 ml of double distilled H2O (resistivity about 18 MΩ•cm). Each solution was then transferred to a Teflon container (
volume 100 mL). The Teflon container was sealed, placed in a microwave oven (Milestone, STARTSynth, HPR-1000-10S segment with temperature and pressure control), heated to 220 °C and then maintained at this temperature by powering the oven with a maximum power of 900 W for a total irradiation time of 2 minutes. After cooling to room temperature, the suspended product in each container was separated by centrifugation and washed twice with double-distilled H2O and subsequently once with ethanol. Each powder sample was finally dried under vacuum at 60 °C overnight. - In addition to ICP-OES analysis, the samples of the invention were examined by scanning electron microscopy and EDX analysis to determine the morphology (also for Cu and Sb samples) and the antimony distribution, by X-ray diffraction to determine the crystal structure (also for Cu and Sb samples) and by XPS to determine the oxidation state of Cu and Sb; the results of the three analyses have been discussed above with reference to
Figures 1 ,2 and3 respectively. - This example relates to the production of electrodes for electrochemical CO2 reduction using the materials of the invention (samples A-H) and the three comparison materials (samples Cu, Sb and NI).
- Each electrode was prepared by mixing 10 mg of sample A-H, Cu, Sb or NI, 1 mg of carbon black from acetylene, 90 µl of Nafion® 117 solution and 320 µl of isopropanol. Each mixture was sonicated for 30 minutes until a uniform suspension was obtained. Each suspension was then used to coat a carbon paper covered with a gas permeable layer (GDL; SIGRACET 28BC, SGL Technologies); the geometric area of each electrode was 1.5 cm2. The obtained electrode was dried at 60 °C overnight to evaporate the solvents. The electrocatalyst loading on each electrode was approximately 3.0 mg cm-2. The electrodes thus obtained are referred to in the following by the abbreviations Ex, where the subscript x corresponds to the sample A-H, Cu, Sb or NI used for its production.
- This example refers to the measurement of the CO2 reduction efficiency of the electrodes prepared in the previous Example.
- Electrochemical measurements were performed with a cell having the configuration schematically shown in
Fig. 4 ; the cell as a whole, 10, is shown in the figure enclosed by a discontinuous line. As shown in the figure, the cell has two compartments separated by an ion exchange membrane 11 (Nafion® N117 membrane, Sigma-Aldrich), and adopts a three-electrode configuration. Each compartment has a total volume of 10 ml and contains 7 ml of electrolyte, and thus 3 ml of headspace. The reference electrode, 12, is an Ag/AgCl electrode (1 mm, lossless LF-1) that is inserted into the cathode compartment. The counter electrode, 13, is a Pt foil (Goodfellow, 99.95%). The working electrode, i.e., the electrode of the invention, is shown in the figure aselement 14. An aqueous solution of 0.1 M KHCO3 was used as the electrolyte solution. In this configuration, gaseous CO2 is fed into both half-cells from the lower part of the two compartments, while the mixture of products on which the results are evaluated is extracted from the cathode compartment (on the right in the figure); most of this mixture is sent to the separation and purification stage (performed with methods known in the field and not described in this text), while a fraction of the mixture is sent to the analysis. Chronoamperometric measurements were performed using a CHI760D electrochemical workstation (CH Instruments, Inc., USA). Gas phase products were analysed in real time with a microgascromatograph (µGC). The inlet of the µGC instrument was connected to the cathode side of the electrochemical cell through a GENIE filter, to remove humidity from the gas before it entered the analysis instrument (µGC). During the chronoamperometric measurements, the electrolytes on both sides of the anode and cathode were static, while a constant CO2 flow rate of 15 ml/min was maintained to saturate the cathode electrolyte and to bring the gaseous products to the µGC. The tests were performed at different potentials between -0.79 V and -0.99 V. The potential was corrected by compensating for the ohmic potential drop, 85% of which was from the instrument (iR compensation). - Selectivity is described by the faradic efficiency (FE), which is the ratio of the amount of charge (coulomb, C) required to produce a certain amount of a product to the total charge consumed over the reaction time, and is expressed by the following equation:
- The results of the tests at two potential values are shown in Table 2.
Table 2 Electrode Potential -0.79 V Potential -0.99 V FECO (%) FEH2 (%) FECO (%) FEH2 (%) ECu 9.5 90 8.5 85 EA 87 14 73 26 EB 85 13 84 15 EC 90 8.5 81 18 ED 90 8 92 7 EE 91 8.5 90 8 EF 90 10.5 89 9.5 EG 89 10 85 14 EH 83.8 16.5 68.5 33 ENI 55 43 62 37 ESb 0 63 0 83 - As can be seen from the test results, the ESb electrode does not produce CO at either test potential. The Cu electrode has poor selectivity for CO, with FECO values below 10%. The comparison ENI electrode shows poor selectivity values towards CO, probably because it is formed by a mixture containing only a small amount of active material together with a completely inactive material (antimony oxide). In contrast, the EA-EH electrodes of the invention exhibit high selectivity towards CO, with FEco above 80% for all A-H materials at -0.79 V. Among these materials, in particular, D and E show excellent selectivity values for CO, of at least 90% at both potentials.
- This example relates to the measurement of CO2 reduction with an electrode of the invention at various potentials.
- The ED electrode, which gave the best results in Example 3, was tested at five different potential values ranging from -0.69 V to -1.09 V. In each test, the evolution of CO and H2 over time was evaluated during tests lasting between one and two hours.
- The results of these tests are shown graphically in
Fig. 5 . In detail,Figures 5(a) to 5(e) report tests performed at the following potentials: 5(a) -0.69 V; 5(b) -0.79 V; 5(c) -0.89 V; 5(d) -0.99 V; 5(e) -1.09 V. The tests at -0.79 V and -0.99 V are the same as those whose results have already been reported in the previous example. The results of these tests are provided in summary form in the graph inFig. 5(f) , in which the faradic efficiency values for CO and H2, taken when the reduction process has reached steady state, are reported at all evaluated potentials. - As can be seen in the graphs (
Figs. 5(a)-(e) ), in each test there is an initial settling time between about 10 minutes (test at -0.99 V) and 20 minutes; this is attributed to stabilization of the electrode and filling of the headspace of the electrochemical cell and of tubes between the cell and the µGC. Then, the FE values stabilize, indicating the stable performance of the electrode. The ED electrode shows very good performance in the conversion of CO2 to CO (FECO > 80%) over the whole range of potentials explored, with values up to 90-92% at potentials from -0.79 V to -1.09 V. At more negative potentials (< -1.09 V), FEco falls below 90%. FEH2 values remain low (≤ 9%) from -0.69 V to -1.09 V. No other gas phase products other than CO and H2 were detected. Liquid products (e.g., HCOOH) were not quantified, but can be assumed to be present in very small or negligible amounts, since the total faradic efficiency for CO and H2 measured in all tests is around 100%. - As demonstrated in the tests described above, the electrocatalyst materials of the invention catalyze the electrochemical reduction of CO2 with high selectivity toward CO. The materials of the invention then offer further advantages.
- Firstly, antimony and copper, and the compounds thereof used as precursors in the process of the invention, are inexpensive materials; moreover, the production of these materials is simple and easily scalable at an industrial level, also because it does not employ toxic or harmful products; the invention therefore offers a technically viable and competitive alternative to the use of metals such as Au, Ag and Pd.
- Since the materials of the invention are in powder form, they can be used in reactors with various configurations as a gas diffusion electrode (GDE) and different sizes.
Claims (12)
- Electrocatalyst material consisting of copper(I) oxide (Cu2O) containing antimony, wherein the amount of antimony is between 5% to 30% by weight.
- Electrocatalyst material according to claim 1, wherein the amount of antimony is between 5.2% and 26.4% by weight.
- Electrocatalyst material according to claim 2, wherein the amount of antimony is between 17.2% and 23.9% by weight.
- Electrode comprising powder of an electrocatalyst material of any one of claims 1 to 3 and a conductive material deposited on a support, in a weight ratio between electrocatalyst material and conductive material between 9:1 and 19:1.
- Electrode according to claim 4, wherein the conductive material is in the form of powder.
- Electrode according to any one of claims 4 or 5 wherein the conductive material is carbon based.
- Electrode according to claim 6, wherein the conductive material is chosen from carbon black, graphite, graphene, carbon nanotubes and mixtures thereof.
- Electrode according to any one of claims 4 to 7 wherein the support is selected from conductive carbon paper, conductive carbon cloth and metal mesh.
- Electrode according to any one of claims 4 to 8 wherein the powder of the electrocatalyst material and possibly of the conductive material are stabilized on the support with an ionomer.
- Process for the production of the electrocatalyst material of any one of claims 1 to 3, comprising the following steps:a) dissolving a copper(II) salt and an antimony(III) salt in a solvent selected from ethanol, ethylene glycol, acetylacetone, diethylamine, ethylenediamine, oleylamine, N,N-dimethylformamide, mixtures of these solvents with each other, with water or with aqueous solutions of D-glucose, hydrazine hydrate, amino acids or sodium carboxymethylcellulose, obtaining a solution;b) heating the solution in a microwave oven at a temperature between 180 and 230 °C for a time between 1 and 10 minutes;c) separating the precipitate from the solution and its drying.
- Process according to claim 10, wherein the copper(II) salt is selected from acetate, sulfate and nitrate, and the antimony(III) salt is selected from acetate, sulfate and nitrate.
- Method for the selective electrochemical reduction of CO2 to CO, comprising the use of an electrode of any one of claims 4 to 9 at a potential between -0.69 V to -1.09 V.
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PCT/IB2021/053074 WO2021209920A1 (en) | 2020-04-15 | 2021-04-14 | Copper and antimony based material and electrode for the selective conversion of carbon dioxide to carbon monoxide |
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