CA3085243A1 - Catalyst system for catalyzed electrochemical reactions and preparation thereof, applications and uses thereof - Google Patents
Catalyst system for catalyzed electrochemical reactions and preparation thereof, applications and uses thereof Download PDFInfo
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- CA3085243A1 CA3085243A1 CA3085243A CA3085243A CA3085243A1 CA 3085243 A1 CA3085243 A1 CA 3085243A1 CA 3085243 A CA3085243 A CA 3085243A CA 3085243 A CA3085243 A CA 3085243A CA 3085243 A1 CA3085243 A1 CA 3085243A1
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- CA
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- Prior art keywords
- gas
- carbon dioxide
- bismuth
- indium
- catalyst system
- Prior art date
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- Pending
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 69
- 238000003487 electrochemical reaction Methods 0.000 title claims abstract description 8
- 238000002360 preparation method Methods 0.000 title description 4
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 122
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 61
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 58
- 238000009792 diffusion process Methods 0.000 claims abstract description 39
- 229910052797 bismuth Inorganic materials 0.000 claims abstract description 34
- 229910052738 indium Inorganic materials 0.000 claims abstract description 33
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims abstract description 32
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims abstract description 29
- 150000001735 carboxylic acids Chemical class 0.000 claims abstract description 9
- 150000007942 carboxylates Chemical class 0.000 claims abstract description 5
- 238000000034 method Methods 0.000 claims description 17
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 13
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 12
- 229910052799 carbon Inorganic materials 0.000 claims description 11
- BDAGIHXWWSANSR-UHFFFAOYSA-M Formate Chemical compound [O-]C=O BDAGIHXWWSANSR-UHFFFAOYSA-M 0.000 claims description 10
- 239000007788 liquid Substances 0.000 claims description 10
- 239000011230 binding agent Substances 0.000 claims description 9
- 239000000758 substrate Substances 0.000 claims description 9
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 7
- 230000002209 hydrophobic effect Effects 0.000 claims description 5
- 239000012736 aqueous medium Substances 0.000 claims description 4
- 239000007795 chemical reaction product Substances 0.000 claims description 4
- 235000019253 formic acid Nutrition 0.000 claims description 4
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 3
- 235000006408 oxalic acid Nutrition 0.000 claims description 3
- 239000002245 particle Substances 0.000 claims description 3
- 238000006243 chemical reaction Methods 0.000 abstract description 16
- 239000000126 substance Substances 0.000 abstract description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 22
- 239000000047 product Substances 0.000 description 22
- 239000007789 gas Substances 0.000 description 17
- 239000000543 intermediate Substances 0.000 description 15
- 229910052751 metal Inorganic materials 0.000 description 14
- 239000002184 metal Substances 0.000 description 14
- 238000006722 reduction reaction Methods 0.000 description 14
- 230000009467 reduction Effects 0.000 description 13
- -1 heterocyclic amine Chemical class 0.000 description 10
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 9
- 238000004519 manufacturing process Methods 0.000 description 9
- 239000000243 solution Substances 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 229910052739 hydrogen Inorganic materials 0.000 description 7
- 239000001257 hydrogen Substances 0.000 description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 229910052760 oxygen Inorganic materials 0.000 description 6
- 239000001301 oxygen Substances 0.000 description 6
- MPZNMEBSWMRGFG-UHFFFAOYSA-N bismuth indium Chemical compound [In].[Bi] MPZNMEBSWMRGFG-UHFFFAOYSA-N 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 239000012279 sodium borohydride Substances 0.000 description 5
- 229910000033 sodium borohydride Inorganic materials 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 4
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 4
- 238000000605 extraction Methods 0.000 description 4
- 238000012216 screening Methods 0.000 description 4
- 239000000725 suspension Substances 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 229910045601 alloy Inorganic materials 0.000 description 3
- 239000000956 alloy Substances 0.000 description 3
- 229910052793 cadmium Inorganic materials 0.000 description 3
- 150000001768 cations Chemical class 0.000 description 3
- 239000010411 electrocatalyst Substances 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- 239000008151 electrolyte solution Substances 0.000 description 3
- 150000002334 glycols Chemical class 0.000 description 3
- 125000000623 heterocyclic group Chemical group 0.000 description 3
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- 239000003014 ion exchange membrane Substances 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 239000002594 sorbent Substances 0.000 description 3
- OISVCGZHLKNMSJ-UHFFFAOYSA-N 2,6-dimethylpyridine Chemical compound CC1=CC=CC(C)=N1 OISVCGZHLKNMSJ-UHFFFAOYSA-N 0.000 description 2
- HNXQXTQTPAJEJL-UHFFFAOYSA-N 2-aminopteridin-4-ol Chemical compound C1=CN=C2NC(N)=NC(=O)C2=N1 HNXQXTQTPAJEJL-UHFFFAOYSA-N 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical class OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N Furan Chemical compound C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 description 2
- 229910000846 In alloy Inorganic materials 0.000 description 2
- SIKJAQJRHWYJAI-UHFFFAOYSA-N Indole Chemical compound C1=CC=C2NC=CC2=C1 SIKJAQJRHWYJAI-UHFFFAOYSA-N 0.000 description 2
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 2
- 150000001450 anions Chemical class 0.000 description 2
- 230000005587 bubbling Effects 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- PPNKDDZCLDMRHS-UHFFFAOYSA-N dinitrooxybismuthanyl nitrate Chemical compound [Bi+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O PPNKDDZCLDMRHS-UHFFFAOYSA-N 0.000 description 2
- 238000000909 electrodialysis Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 229910052745 lead Inorganic materials 0.000 description 2
- 238000000622 liquid--liquid extraction Methods 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 2
- 238000000638 solvent extraction Methods 0.000 description 2
- 229910052718 tin Inorganic materials 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- GCNTZFIIOFTKIY-UHFFFAOYSA-N 4-hydroxypyridine Chemical compound OC1=CC=NC=C1 GCNTZFIIOFTKIY-UHFFFAOYSA-N 0.000 description 1
- GFFGJBXGBJISGV-UHFFFAOYSA-N Adenine Chemical compound NC1=NC=NC2=C1N=CN2 GFFGJBXGBJISGV-UHFFFAOYSA-N 0.000 description 1
- 229930024421 Adenine Natural products 0.000 description 1
- 229910000851 Alloy steel Inorganic materials 0.000 description 1
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- ROFVEXUMMXZLPA-UHFFFAOYSA-N Bipyridyl Chemical compound N1=CC=CC=C1C1=CC=CC=N1 ROFVEXUMMXZLPA-UHFFFAOYSA-N 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- 239000004471 Glycine Substances 0.000 description 1
- AEMRFAOFKBGASW-UHFFFAOYSA-M Glycolate Chemical compound OCC([O-])=O AEMRFAOFKBGASW-UHFFFAOYSA-M 0.000 description 1
- 229910020451 K2SiO3 Inorganic materials 0.000 description 1
- JVTAAEKCZFNVCJ-UHFFFAOYSA-M Lactate Chemical compound CC(O)C([O-])=O JVTAAEKCZFNVCJ-UHFFFAOYSA-M 0.000 description 1
- 239000007832 Na2SO4 Substances 0.000 description 1
- 229910003296 Ni-Mo Inorganic materials 0.000 description 1
- ZCQWOFVYLHDMMC-UHFFFAOYSA-N Oxazole Chemical compound C1=COC=N1 ZCQWOFVYLHDMMC-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 229920000388 Polyphosphate Polymers 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- FZWLAAWBMGSTSO-UHFFFAOYSA-N Thiazole Chemical compound C1=CSC=N1 FZWLAAWBMGSTSO-UHFFFAOYSA-N 0.000 description 1
- DGEZNRSVGBDHLK-UHFFFAOYSA-N [1,10]phenanthroline Chemical compound C1=CN=C2C3=NC=CC=C3C=CC2=C1 DGEZNRSVGBDHLK-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 229960000643 adenine Drugs 0.000 description 1
- 150000003973 alkyl amines Chemical class 0.000 description 1
- 230000004075 alteration Effects 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
- 125000006615 aromatic heterocyclic group Chemical group 0.000 description 1
- 229910052792 caesium Inorganic materials 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 235000011148 calcium chloride Nutrition 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000000254 damaging effect Effects 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- HPYNZHMRTTWQTB-UHFFFAOYSA-N dimethylpyridine Natural products CC1=CC=CN=C1C HPYNZHMRTTWQTB-UHFFFAOYSA-N 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 150000004675 formic acid derivatives Chemical class 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000003517 fume Substances 0.000 description 1
- HHLFWLYXYJOTON-UHFFFAOYSA-N glyoxylic acid Chemical compound OC(=O)C=O HHLFWLYXYJOTON-UHFFFAOYSA-N 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- PZOUSPYUWWUPPK-UHFFFAOYSA-N indole Natural products CC1=CC=CC2=C1C=CN2 PZOUSPYUWWUPPK-UHFFFAOYSA-N 0.000 description 1
- RKJUIXBNRJVNHR-UHFFFAOYSA-N indolenine Natural products C1=CC=C2CC=NC2=C1 RKJUIXBNRJVNHR-UHFFFAOYSA-N 0.000 description 1
- 239000003317 industrial substance Substances 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 229910001092 metal group alloy Inorganic materials 0.000 description 1
- 239000006262 metallic foam Substances 0.000 description 1
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 description 1
- 239000012229 microporous material Substances 0.000 description 1
- 230000000116 mitigating effect Effects 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 238000001728 nano-filtration Methods 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 239000008239 natural water Substances 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 150000002826 nitrites Chemical class 0.000 description 1
- 239000012457 nonaqueous media Substances 0.000 description 1
- 238000012261 overproduction Methods 0.000 description 1
- 239000011236 particulate material Substances 0.000 description 1
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical class OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000001205 polyphosphate Substances 0.000 description 1
- 235000011176 polyphosphates Nutrition 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 239000005373 porous glass Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011736 potassium bicarbonate Substances 0.000 description 1
- 235000015497 potassium bicarbonate Nutrition 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
- 238000012545 processing Methods 0.000 description 1
- CPNGPNLZQNNVQM-UHFFFAOYSA-N pteridine Chemical compound N1=CN=CC2=NC=CN=C21 CPNGPNLZQNNVQM-UHFFFAOYSA-N 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910052701 rubidium Inorganic materials 0.000 description 1
- 239000013535 sea water Substances 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000001509 sodium citrate Substances 0.000 description 1
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 description 1
- 235000010344 sodium nitrate Nutrition 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 230000007928 solubilization Effects 0.000 description 1
- 238000005063 solubilization Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 235000011149 sulphuric acid Nutrition 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- HRXKRNGNAMMEHJ-UHFFFAOYSA-K trisodium citrate Chemical compound [Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O HRXKRNGNAMMEHJ-UHFFFAOYSA-K 0.000 description 1
- 235000019263 trisodium citrate Nutrition 0.000 description 1
- 229940038773 trisodium citrate Drugs 0.000 description 1
- 239000011800 void 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
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
-
- 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
- C25B3/00—Electrolytic production of organic compounds
- C25B3/01—Products
- C25B3/07—Oxygen containing compounds
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B3/00—Electrolytic production of organic compounds
- C25B3/20—Processes
- C25B3/25—Reduction
- C25B3/26—Reduction of carbon dioxide
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
Abstract
A catalyst system for catalyzed electrochemical reactions, in particular the electrochemical conversion of carbon dioxide into valuable chemical products, such as carboxylates and carboxylic acids, comprises a catalyst, wherein the catalyst comprises bismuth and indium. The catalyst system can be a component of a gas diffusion electrode, that can be used as the cathode electrode in an electrochemical cell.
Description
CATALYST SYSTEM FOR CATALYZED ELECTROCHEMICAL REACTIONS AND
PREPARATION THEREOF, APPLICATIONS AND USES THEREOF
The present invention generally relates to a catalyst system for catalyzed electrochemical reactions, comprising a conductive support and a catalyst, in particular for reducing carbon dioxide in order to prepare products or intermediates thereof like carboxylates and/or carboxylic acids.
The electrochemical conversion of carbon dioxide into economically valuable materials such as fuels and industrial chemicals or intermediate products thereof is gaining interest in view of mitigating the emission of carbon dioxide into the atmosphere, which is responsible for climate alterations, changes in pH of seawater and other potentially damaging effects like melting of polar ice and sea level rise.
Catalyzed electrochemical reduction of carbon dioxide for preparing economically valuable products is known in the art.
E.g. W02013/006711 discloses methods and systems for the electrochemical conversion of carbon dioxide to products like carboxylic acids, glycols and carboxylates in the presence of a homogeneous heterocyclic amine catalyst. In an embodiment the cathode of the electrochemical cell wherein the conversion is performed, comprises a material suitable for the reduction of carbon dioxide. Examples of the cathode materials include metal and metal alloys, amongst others indium and indium alloys.
W02014/032000 discloses a method of reducing carbon dioxide into one or more organic products in an electrochemical cell, wherein the cathode is an oxidized indium electrode, in particular an anodized indium electrode.
W02014/042781 discloses the electrochemical conversion of carbon dioxide into products using a high surface area cathode, wherein the cathode includes an indium coating and has a void volume of between about 30% to 98%. The cathode may also include indium coatings and/or metal structures further containing Pb, Sn, Hg, TI, In, Bi, and Cd, their alloys, and combinations thereof. Metals including Ti, Nb, Cr, Mo, Ag, Cd, Hg, TI, An, and Pb as well as Cr-Ni-Mo steel alloys among many others may be incorporated. The alloys of indium with other metals, including Sn, Pb, Hg, TI, Bi, Cu, and Cd and their mixed alloys and combinations thereof on the exposed catalytic surfaces of the electrode preferably comprise 5% to 99% indium.
PREPARATION THEREOF, APPLICATIONS AND USES THEREOF
The present invention generally relates to a catalyst system for catalyzed electrochemical reactions, comprising a conductive support and a catalyst, in particular for reducing carbon dioxide in order to prepare products or intermediates thereof like carboxylates and/or carboxylic acids.
The electrochemical conversion of carbon dioxide into economically valuable materials such as fuels and industrial chemicals or intermediate products thereof is gaining interest in view of mitigating the emission of carbon dioxide into the atmosphere, which is responsible for climate alterations, changes in pH of seawater and other potentially damaging effects like melting of polar ice and sea level rise.
Catalyzed electrochemical reduction of carbon dioxide for preparing economically valuable products is known in the art.
E.g. W02013/006711 discloses methods and systems for the electrochemical conversion of carbon dioxide to products like carboxylic acids, glycols and carboxylates in the presence of a homogeneous heterocyclic amine catalyst. In an embodiment the cathode of the electrochemical cell wherein the conversion is performed, comprises a material suitable for the reduction of carbon dioxide. Examples of the cathode materials include metal and metal alloys, amongst others indium and indium alloys.
W02014/032000 discloses a method of reducing carbon dioxide into one or more organic products in an electrochemical cell, wherein the cathode is an oxidized indium electrode, in particular an anodized indium electrode.
W02014/042781 discloses the electrochemical conversion of carbon dioxide into products using a high surface area cathode, wherein the cathode includes an indium coating and has a void volume of between about 30% to 98%. The cathode may also include indium coatings and/or metal structures further containing Pb, Sn, Hg, TI, In, Bi, and Cd, their alloys, and combinations thereof. Metals including Ti, Nb, Cr, Mo, Ag, Cd, Hg, TI, An, and Pb as well as Cr-Ni-Mo steel alloys among many others may be incorporated. The alloys of indium with other metals, including Sn, Pb, Hg, TI, Bi, Cu, and Cd and their mixed alloys and combinations thereof on the exposed catalytic surfaces of the electrode preferably comprise 5% to 99% indium.
2 Preliminary research has indicated that not all the potential catalysts as disclosed in the above prior art documents function as desired in terms of selectivity, activity and Faradaic efficiency.
Therefore there is an ongoing need to develop catalyst systems, which show an improvement of one or more of these catalyst properties.
In particular the present invention aims at providing a catalyst system having a high Faradaic efficiency for the electrochemical reduction of carbon dioxide and a high selectivity towards valuable reduction products, in particular carboxylic acids or intermediates thereof, such as carboxylate salts.
This invention provides a catalyst system for catalyzed electrochemical reactions, comprising a catalyst, wherein the catalyst comprises 5-94 wt.% bismuth and 6-95 wt.%
indium, based on the total amount of bismuth and indium. This catalyst will herein below be referred to as an indium bismuth catalyst.
The catalyst system according to the invention for catalyzed electrochemical reactions, in particular reduction of carbon dioxide, preferably comprises an electrically conductive support and a catalyst, wherein the catalyst comprises 5-94 wt.% bismuth and 6-95 wt.%
indium, based on the total amount of bismuth and indium.
Surprisingly it has been found that the binary metal combination of bismuth and indium as catalyst for the electrochemical conversion of carbon dioxide shows a good selectivity for the reduction of carbon dioxide into carboxylic acids and carboxylates, as well as a good Faradaic yield, in particular for the aqueous conversion of carbon dioxide to formate salt.
Compared to other indium based binary metal catalysts the indium bismuth catalyst shows an improved Faradaic yield. The amount of bismuth is in the range of 5-94 wt.%
based on the total amount of bismuth and indium, preferably in the range of 10-90 wt.%, more preferably 30-90 wt.%, such as 35-90 wt.%. Experimental results have indicated that an amount of bismuth in the range of 40-60 wt.%, such as 45-55 wt.%, e.g. about 1:1 weight ratio of bismuth to indium, offers improved catalytic properties regarding carbon dioxide to formate conversion.
The catalyst can comprise a combination of bismuth and indium in different thermodynamic phases. Preferably an amorphous combination of bismuth and indium is used.
That is, preferably the catalyst system according to the invention comprises a catalyst, wherein the catalyst comprises an amorphous combination of 5-94 wt.% bismuth and 6-95 wt.% indium, based on the total amount of bismuth and indium.
The indium bismuth catalyst according to the invention can be applied without or in combination with an electrically conductive support. It can, for example, be applied without or in combination with a carbon containing support. Preferably the indium bismuth catalyst is applied in
Therefore there is an ongoing need to develop catalyst systems, which show an improvement of one or more of these catalyst properties.
In particular the present invention aims at providing a catalyst system having a high Faradaic efficiency for the electrochemical reduction of carbon dioxide and a high selectivity towards valuable reduction products, in particular carboxylic acids or intermediates thereof, such as carboxylate salts.
This invention provides a catalyst system for catalyzed electrochemical reactions, comprising a catalyst, wherein the catalyst comprises 5-94 wt.% bismuth and 6-95 wt.%
indium, based on the total amount of bismuth and indium. This catalyst will herein below be referred to as an indium bismuth catalyst.
The catalyst system according to the invention for catalyzed electrochemical reactions, in particular reduction of carbon dioxide, preferably comprises an electrically conductive support and a catalyst, wherein the catalyst comprises 5-94 wt.% bismuth and 6-95 wt.%
indium, based on the total amount of bismuth and indium.
Surprisingly it has been found that the binary metal combination of bismuth and indium as catalyst for the electrochemical conversion of carbon dioxide shows a good selectivity for the reduction of carbon dioxide into carboxylic acids and carboxylates, as well as a good Faradaic yield, in particular for the aqueous conversion of carbon dioxide to formate salt.
Compared to other indium based binary metal catalysts the indium bismuth catalyst shows an improved Faradaic yield. The amount of bismuth is in the range of 5-94 wt.%
based on the total amount of bismuth and indium, preferably in the range of 10-90 wt.%, more preferably 30-90 wt.%, such as 35-90 wt.%. Experimental results have indicated that an amount of bismuth in the range of 40-60 wt.%, such as 45-55 wt.%, e.g. about 1:1 weight ratio of bismuth to indium, offers improved catalytic properties regarding carbon dioxide to formate conversion.
The catalyst can comprise a combination of bismuth and indium in different thermodynamic phases. Preferably an amorphous combination of bismuth and indium is used.
That is, preferably the catalyst system according to the invention comprises a catalyst, wherein the catalyst comprises an amorphous combination of 5-94 wt.% bismuth and 6-95 wt.% indium, based on the total amount of bismuth and indium.
The indium bismuth catalyst according to the invention can be applied without or in combination with an electrically conductive support. It can, for example, be applied without or in combination with a carbon containing support. Preferably the indium bismuth catalyst is applied in
3 combination with an electrically conductive support. Therefore, the catalyst system is preferably a catalyst system for catalyzed electrochemical reactions, comprising an electrically conductive support and a catalyst, wherein the catalyst comprises 5-94 wt.% bismuth and 6-95 wt.% indium, based on the total amount of bismuth and indium.
As a conductive support a particulate material, in particular carbon particles, is used. Preferably the conductive support comprises a porous structure of carbon particles bonded together. A
preferred binding material is a hydrophobic binder, such as a fluorinated binder. The catalyst is deposited onto or adhered to the conductive material. The weight ratio of indium and bismuth to carbon can advantageously be in the range of 0.10-1.50, e.g. about 30 wt.%.
Typically, the electrochemical reduction of carbon dioxide into chemical reduction products is performed in an electrochemical cell or photochemical cell having at least two cell compartments containing the respective electrodes. Carbon dioxide is supplied to the cathode. The cathode is preferably a gas-diffusion electrode providing a high surface area or interface for solid-liquid-gas contact. Such a gas-diffusion electrode comprises an electrically conductive substrate, which may serve as a supporting structure for a gas-diffusion layer. The gas-diffusion layer provides a thin porous structure or network e.g. made from carbon, for passing a gas like carbon dioxide from one side to the other. Typically the structure is hydrophobic to distract water. The gas-diffusion layer may comprise a catalytically active material.
Therefor a further aspect of the invention relates to a gas-diffusion electrode, comprising a gas-diffusion layer on an electrically conductive substrate, wherein the gas-diffusion layer comprises the catalyst system according to the invention as outlined above. The binary metal catalyst system of bismuth and indium according to the invention may be embedded in the gas-diffusion layer structure or provided as one or more additional separate layers thereof.
As explained above, a particulate carbon is a preferred example of the conductive support for the catalyst.
The catalyst system is preferably bonded to the electrically conductive substrate using a hydrophobic binder such as PTFE. Examples of suitable substrates include metal structures like expanded or woven metals, metal foams, and carbon structures including wovens, cloth and paper.
Yet another aspect of the invention is an electrochemical cell comprising at least one gas chamber and at least one liquid chamber, which chambers are separated by a gas-diffusion electrode according to the invention.
Generally the reduction of carbon dioxide is performed in an electrochemical cell, typically a divided cell having two cell compartments. One cell compartment contains the anode, and the other cell compartment contains a gas-diffusion cathode electrode according to the invention,
As a conductive support a particulate material, in particular carbon particles, is used. Preferably the conductive support comprises a porous structure of carbon particles bonded together. A
preferred binding material is a hydrophobic binder, such as a fluorinated binder. The catalyst is deposited onto or adhered to the conductive material. The weight ratio of indium and bismuth to carbon can advantageously be in the range of 0.10-1.50, e.g. about 30 wt.%.
Typically, the electrochemical reduction of carbon dioxide into chemical reduction products is performed in an electrochemical cell or photochemical cell having at least two cell compartments containing the respective electrodes. Carbon dioxide is supplied to the cathode. The cathode is preferably a gas-diffusion electrode providing a high surface area or interface for solid-liquid-gas contact. Such a gas-diffusion electrode comprises an electrically conductive substrate, which may serve as a supporting structure for a gas-diffusion layer. The gas-diffusion layer provides a thin porous structure or network e.g. made from carbon, for passing a gas like carbon dioxide from one side to the other. Typically the structure is hydrophobic to distract water. The gas-diffusion layer may comprise a catalytically active material.
Therefor a further aspect of the invention relates to a gas-diffusion electrode, comprising a gas-diffusion layer on an electrically conductive substrate, wherein the gas-diffusion layer comprises the catalyst system according to the invention as outlined above. The binary metal catalyst system of bismuth and indium according to the invention may be embedded in the gas-diffusion layer structure or provided as one or more additional separate layers thereof.
As explained above, a particulate carbon is a preferred example of the conductive support for the catalyst.
The catalyst system is preferably bonded to the electrically conductive substrate using a hydrophobic binder such as PTFE. Examples of suitable substrates include metal structures like expanded or woven metals, metal foams, and carbon structures including wovens, cloth and paper.
Yet another aspect of the invention is an electrochemical cell comprising at least one gas chamber and at least one liquid chamber, which chambers are separated by a gas-diffusion electrode according to the invention.
Generally the reduction of carbon dioxide is performed in an electrochemical cell, typically a divided cell having two cell compartments. One cell compartment contains the anode, and the other cell compartment contains a gas-diffusion cathode electrode according to the invention,
4 comprising the binary metal electrocatalyst of bismuth and indium. The two cell compartments may be separated by a suitable membrane, e.g. made from porous glass frit, microporous material, ion exchanging membrane or ion conducting bridge, allowing ionic species to travel from one compartment to the other, such as protons generated at the anode to the cathode compartment.
A further aspect of the invention concerns a method of preparing a gas-diffusion electrode as defined above, comprising the binary metal electrocatalyst system according to the invention.
This manufacturing method comprises a step of providing an electrically conductive substrate and a step of applying the catalyst system according to the invention, comprising indium and bismuth and an electrically conductive support, in particular particulate support material, and a binder to the gas-diffusion layer of the gas-diffusion electrode.
The electrocatalyst loaded gas-diffusion electrode can be manufactured in various ways including spraying, casting and sintering, often using one or more suitable binders.
The invention also relates to a method of electrocatalytically converting carbon dioxide into valuable products or product intermediates. This method comprises:
introducing an anolyte to a first cell compartment of an electrochemical cell, the first cell compartment comprising an anode;
introducing a catholyte and carbon dioxide to a second cell compartment of the electrochemical cell, the second cell compartment comprising a cathode, and applying an electrical potential between the anode and the cathode sufficient to reduce carbon dioxide to a reduced reaction product, wherein the cathode comprises a catalyst system according to the invention, in particular the cathode is a gas-diffusion electrode according to the invention.
The method according to the invention allows to reduce carbon dioxide to carboxylic acid and intermediates, including salts such as formate, glycolate, glyoxylate, oxalate and lactate, carboxylic acids, and glycols. The production of a carboxylic acid or carboxylic acid intermediate may be dependent on the pH of the electrolyte solution in the cell, with lower pH ranges favoring carboxylic acid production. The pH of the cathode compartment may be adjusted to favor production of one of a carboxylic acid or carboxylic acid intermediate over production of the other, such as by introducing an acid (e.g., HCI or H2SO4) to the cathode compartment. The pH
of the catholyte is preferably between about 1 and 8. A pH range of 1-4 is preferable for production of carboxylic acids from carbon dioxide. A pH range of 4-8 is preferable for production of carboxylic acid intermediates from carbon dioxide.
The electrical potential may be a DC voltage. In preferred embodiments, the applied electrical potential is generally between about -1.5V vs. SCE and about -6V vs. SCE, preferably from about -1.5V vs. SCE to about -5V vs. SCE, such as in the range of -3V vs. SCE
to -5V vs SCE
and more preferably from about -1.5V vs. SCE to about -4V vs. SCE.
A further aspect of the invention concerns a method of preparing a gas-diffusion electrode as defined above, comprising the binary metal electrocatalyst system according to the invention.
This manufacturing method comprises a step of providing an electrically conductive substrate and a step of applying the catalyst system according to the invention, comprising indium and bismuth and an electrically conductive support, in particular particulate support material, and a binder to the gas-diffusion layer of the gas-diffusion electrode.
The electrocatalyst loaded gas-diffusion electrode can be manufactured in various ways including spraying, casting and sintering, often using one or more suitable binders.
The invention also relates to a method of electrocatalytically converting carbon dioxide into valuable products or product intermediates. This method comprises:
introducing an anolyte to a first cell compartment of an electrochemical cell, the first cell compartment comprising an anode;
introducing a catholyte and carbon dioxide to a second cell compartment of the electrochemical cell, the second cell compartment comprising a cathode, and applying an electrical potential between the anode and the cathode sufficient to reduce carbon dioxide to a reduced reaction product, wherein the cathode comprises a catalyst system according to the invention, in particular the cathode is a gas-diffusion electrode according to the invention.
The method according to the invention allows to reduce carbon dioxide to carboxylic acid and intermediates, including salts such as formate, glycolate, glyoxylate, oxalate and lactate, carboxylic acids, and glycols. The production of a carboxylic acid or carboxylic acid intermediate may be dependent on the pH of the electrolyte solution in the cell, with lower pH ranges favoring carboxylic acid production. The pH of the cathode compartment may be adjusted to favor production of one of a carboxylic acid or carboxylic acid intermediate over production of the other, such as by introducing an acid (e.g., HCI or H2SO4) to the cathode compartment. The pH
of the catholyte is preferably between about 1 and 8. A pH range of 1-4 is preferable for production of carboxylic acids from carbon dioxide. A pH range of 4-8 is preferable for production of carboxylic acid intermediates from carbon dioxide.
The electrical potential may be a DC voltage. In preferred embodiments, the applied electrical potential is generally between about -1.5V vs. SCE and about -6V vs. SCE, preferably from about -1.5V vs. SCE to about -5V vs. SCE, such as in the range of -3V vs. SCE
to -5V vs SCE
and more preferably from about -1.5V vs. SCE to about -4V vs. SCE.
5 High Faradaic yield and selectivity of the catalyst system according to the invention for conversion of carbon dioxide into formate/formic acid have been shown at the cathode according to the reaction CO2 + 2H+ + 2e-4 HCOOH, while at the anode water may be oxidized into oxygen and hydrogen ions according to 2H20 4 4H+ + 02 + 4e-.
The hydrogen ions pass through the ion exchange membrane from the anolyte compartment to the catholyte compartment in the electrochemical cell.
The carbon dioxide conversion to formate/formic acid is typically performed in an aqueous medium, wherein the CO2 is bubbled through the aqueous medium or distributed to the gas-diffusion electrode, e.g. using perculator systems.
Non-aqueous media may also be used, e.g. in the direct conversion of carbon dioxide to oxalic acid or oxalate.
A homogeneous heterocyclic catalyst may be added to the cathode compartment of the cell containing the cathode. The homogeneous heterocyclic catalyst may include, for example, one or more of 4-hydroxy pyridine, adenine, a heterocyclic amine containing sulfur, a heterocyclic amine containing oxygen, an azole, a benzinnidazole, a bipyridine, furan, an innidazole, an imidazole related species with at least one five-member ring, an indole, a lutidine, nnethylinnidazole, an oxazole, phenanthroline, pterin, pteridine, a pyridine, a pyridine related species with at least one six-member ring, pyrrole, quinoline, or a thiazole, and mixtures thereof.
If present, the homogeneous heterocyclic catalyst is preferably present at a concentration of between about 0.001M and about 1M, and more preferably between about 0.01M and 0.5M.
The chemicals derived as reaction products from the direct electrochemical conversion according to the invention can be processed further into industrial products.
E.g. oxalic acid can be used as a starting material for the production of ethylene glycol and/or glycine. See e.g.
U52016/0017503. Hydrogen may be introduced to the carboxylic acid or carboxylic acid intermediate to produce a glycol or a carboxylic acid, respectively. Hydrogen may be derived from natural gas or water.
The invention is further illustrated by the attached drawings and examples.
In the drawings Fig. 1 shows an embodiment of an electrochemical cell according to the invention; and Fig. 2 is an embodiment of a gas-diffusion electrode according to the invention.
The hydrogen ions pass through the ion exchange membrane from the anolyte compartment to the catholyte compartment in the electrochemical cell.
The carbon dioxide conversion to formate/formic acid is typically performed in an aqueous medium, wherein the CO2 is bubbled through the aqueous medium or distributed to the gas-diffusion electrode, e.g. using perculator systems.
Non-aqueous media may also be used, e.g. in the direct conversion of carbon dioxide to oxalic acid or oxalate.
A homogeneous heterocyclic catalyst may be added to the cathode compartment of the cell containing the cathode. The homogeneous heterocyclic catalyst may include, for example, one or more of 4-hydroxy pyridine, adenine, a heterocyclic amine containing sulfur, a heterocyclic amine containing oxygen, an azole, a benzinnidazole, a bipyridine, furan, an innidazole, an imidazole related species with at least one five-member ring, an indole, a lutidine, nnethylinnidazole, an oxazole, phenanthroline, pterin, pteridine, a pyridine, a pyridine related species with at least one six-member ring, pyrrole, quinoline, or a thiazole, and mixtures thereof.
If present, the homogeneous heterocyclic catalyst is preferably present at a concentration of between about 0.001M and about 1M, and more preferably between about 0.01M and 0.5M.
The chemicals derived as reaction products from the direct electrochemical conversion according to the invention can be processed further into industrial products.
E.g. oxalic acid can be used as a starting material for the production of ethylene glycol and/or glycine. See e.g.
U52016/0017503. Hydrogen may be introduced to the carboxylic acid or carboxylic acid intermediate to produce a glycol or a carboxylic acid, respectively. Hydrogen may be derived from natural gas or water.
The invention is further illustrated by the attached drawings and examples.
In the drawings Fig. 1 shows an embodiment of an electrochemical cell according to the invention; and Fig. 2 is an embodiment of a gas-diffusion electrode according to the invention.
6 In FIG. 1 a block diagram of a system 100 is shown in accordance with an embodiment of the present invention. System 100 may be utilized for electrochemical production of carboxylic acid intermediates, carboxylic acids, and glycols from carbon dioxide and water (and hydrogen for glycol production). The system 100 generally comprises an electrochemical cell 102, a liquid source 104, an energy source 106, a carbon dioxide source 108, a product extractor 110 and an extractor 112, the latter in this embodiment for the recovery of oxygen produced at the anode. In an embodiment the liquid source 104 is a water source. In another embodiment the liquid source is an organic solvent source. A product or product mixture may be obtained from the product extractor 110 after extraction. An output gas containing oxygen may be output from the oxygen extractor 112 after extraction.
In the embodiment shown the cell 102 is a divided electrochemical cell. The cell 102 reduces carbon dioxide into products or product intermediates. The reduction may take place by introducing such as bubbling carbon dioxide into an electrolyte solution in the cell 102. At the cathode 120 comprising the catalyst system according to the invention carbon dioxide is reduced into a carboxylic acid or a carboxylic acid intermediate.
The cell 102 generally comprises two or more or cell compartments 114a, 114b, a separator 116 e.g. a ion exchange membrane, an anode 118 in anode cell compartment 114a, and a cathode 120 in cathode cell compartment 114b on an opposite side of the separator 116.
The cathode 120 includes a catalyst system according to the invention suitable for the reduction of carbon dioxide. An electrolyte solution e.g., anolyte 122a and catholyte 122b may fill the respective cell compartments 114a and 114b.
The liquid source 104 preferably includes a water source, such that the liquid source 104 may provide pure water to the cell 102. The liquid source 104 may provide other fluids to the cell 102, including an organic solvent, such as methanol, acetonitrile, and dinnethylfuran. The liquid source 104 may also provide a mixture of an organic solvent and water to the cell 102.
The catholyte 122 may include an aromatic heterocyclic catalyst, e.g. in a concentration of about 10 nnM to 1 M. The electrolyte may also include one or more suitable salts, such as KCI, NaNO3, Na2SO4, NaCL, NaF, NaCI04, KCI04, K2SiO3 or CaCl2, e.g. at a concentration of about 0.5 M.
Other additives may include Group I cations (H, Ii, Na, K, Rb and Cs except Fr), divalent cations (e.g., Ca', Mg', Zn') ammonium, alkylannnnoniunn cations and alkyl amines.
Examples of anions comprise halides, carbonates, bicarbonates, nitrates, nitrites, perchlorates, phosphates, polyphosphates, silicates and sulfates. .Bicarbonate is a preferred anion.
The pH of the cathode compartment 114b is preferably between about 1 and 8.
In the embodiment shown the cell 102 is a divided electrochemical cell. The cell 102 reduces carbon dioxide into products or product intermediates. The reduction may take place by introducing such as bubbling carbon dioxide into an electrolyte solution in the cell 102. At the cathode 120 comprising the catalyst system according to the invention carbon dioxide is reduced into a carboxylic acid or a carboxylic acid intermediate.
The cell 102 generally comprises two or more or cell compartments 114a, 114b, a separator 116 e.g. a ion exchange membrane, an anode 118 in anode cell compartment 114a, and a cathode 120 in cathode cell compartment 114b on an opposite side of the separator 116.
The cathode 120 includes a catalyst system according to the invention suitable for the reduction of carbon dioxide. An electrolyte solution e.g., anolyte 122a and catholyte 122b may fill the respective cell compartments 114a and 114b.
The liquid source 104 preferably includes a water source, such that the liquid source 104 may provide pure water to the cell 102. The liquid source 104 may provide other fluids to the cell 102, including an organic solvent, such as methanol, acetonitrile, and dinnethylfuran. The liquid source 104 may also provide a mixture of an organic solvent and water to the cell 102.
The catholyte 122 may include an aromatic heterocyclic catalyst, e.g. in a concentration of about 10 nnM to 1 M. The electrolyte may also include one or more suitable salts, such as KCI, NaNO3, Na2SO4, NaCL, NaF, NaCI04, KCI04, K2SiO3 or CaCl2, e.g. at a concentration of about 0.5 M.
Other additives may include Group I cations (H, Ii, Na, K, Rb and Cs except Fr), divalent cations (e.g., Ca', Mg', Zn') ammonium, alkylannnnoniunn cations and alkyl amines.
Examples of anions comprise halides, carbonates, bicarbonates, nitrates, nitrites, perchlorates, phosphates, polyphosphates, silicates and sulfates. .Bicarbonate is a preferred anion.
The pH of the cathode compartment 114b is preferably between about 1 and 8.
7 The energy source 106 may include a variable voltage source. The energy source 106 may be operational to generate an electrical potential between the anode 118 and the cathode 120.
The gas source 108 preferably includes a carbon dioxide source, such that the gas source 108 may provide carbon dioxide to the cell 102. E.g. the carbon dioxide is bubbled directly into the compartment 114b containing the cathode 120. For instance, the compartment 114b may include a carbon dioxide input, such as a port 126a configured to be coupled between the carbon dioxide source and the cathode 120.
The carbon dioxide may be obtained from any source, preferably a renewable source. The product extractor 110 may include an organic product and/or inorganic product extractor. The product extractor 110 generally facilitates extraction of one or more products e.g., carboxylic acid, and /or carboxylic acid intermediate from the electrolyte 122. The extraction may occur via one or more of a solid sorbent, carbon dioxide- assisted solid sorbent, liquid-liquid extraction, nanofiltration, crystallization and electrodialysis. The extracted products may be presented through a port 126b of the system 100 for subsequent storage, consumption, and/or processing by other devices and /or processes at A. In an embodiment the carboxylic acid or carboxylic acid intermediate is continuously removed from the cell 102, where cell 102 operates on a continuous basis, such as through a continuous flow-single pass reactor where fresh catholyte and carbon dioxide is fed continuously as the input, and where the output from the reactor is continuously removed. In other embodiments, the carboxylic acid or carboxylic acid intermediate is continuously removed from the catholyte 122 via one or more of adsorbing with a solid sorbent, liquid-liquid extraction, and electrodialysis.
The separated carboxylic acid or carboxylic acid intermediate may be placed in contact with a hydrogen stream at A, e.g. in an additional reactor, to produce a glycol or carboxylic acid, respectively.
Oxygen may be discharged from extractor 112 through port 128.
An embodiment of a gas-diffusion electrode according to the invention is shown in Fig. 2.
Fig. 2 represents a schematic illustration of an electrochemical cell 200 utilizing an anode electrode 202 for the anode reaction, in this specific embodiment a hydrogen gas-diffusion electrode, and a carbon dioxide gas-diffusion electrode 204 for the cathode reaction of reducing carbon dioxide e.g. to formate. The cathode 204 may have a carbon dioxide internal gas plenum 206 in the current collector 208 of the electrode 204 to distribute carbon dioxide evenly into the gas-diffusion electrode. A cathode trickle bed solution distributor or percolator 210 is present in the catholyte cell compartment 212. The catholyte solution may be introduced at the top entry 214 of the catholyte compartment 212 and the catholyte solution is distributed evenly down the
The gas source 108 preferably includes a carbon dioxide source, such that the gas source 108 may provide carbon dioxide to the cell 102. E.g. the carbon dioxide is bubbled directly into the compartment 114b containing the cathode 120. For instance, the compartment 114b may include a carbon dioxide input, such as a port 126a configured to be coupled between the carbon dioxide source and the cathode 120.
The carbon dioxide may be obtained from any source, preferably a renewable source. The product extractor 110 may include an organic product and/or inorganic product extractor. The product extractor 110 generally facilitates extraction of one or more products e.g., carboxylic acid, and /or carboxylic acid intermediate from the electrolyte 122. The extraction may occur via one or more of a solid sorbent, carbon dioxide- assisted solid sorbent, liquid-liquid extraction, nanofiltration, crystallization and electrodialysis. The extracted products may be presented through a port 126b of the system 100 for subsequent storage, consumption, and/or processing by other devices and /or processes at A. In an embodiment the carboxylic acid or carboxylic acid intermediate is continuously removed from the cell 102, where cell 102 operates on a continuous basis, such as through a continuous flow-single pass reactor where fresh catholyte and carbon dioxide is fed continuously as the input, and where the output from the reactor is continuously removed. In other embodiments, the carboxylic acid or carboxylic acid intermediate is continuously removed from the catholyte 122 via one or more of adsorbing with a solid sorbent, liquid-liquid extraction, and electrodialysis.
The separated carboxylic acid or carboxylic acid intermediate may be placed in contact with a hydrogen stream at A, e.g. in an additional reactor, to produce a glycol or carboxylic acid, respectively.
Oxygen may be discharged from extractor 112 through port 128.
An embodiment of a gas-diffusion electrode according to the invention is shown in Fig. 2.
Fig. 2 represents a schematic illustration of an electrochemical cell 200 utilizing an anode electrode 202 for the anode reaction, in this specific embodiment a hydrogen gas-diffusion electrode, and a carbon dioxide gas-diffusion electrode 204 for the cathode reaction of reducing carbon dioxide e.g. to formate. The cathode 204 may have a carbon dioxide internal gas plenum 206 in the current collector 208 of the electrode 204 to distribute carbon dioxide evenly into the gas-diffusion electrode. A cathode trickle bed solution distributor or percolator 210 is present in the catholyte cell compartment 212. The catholyte solution may be introduced at the top entry 214 of the catholyte compartment 212 and the catholyte solution is distributed evenly down the
8 cell and is discharged via exit 216 at the bottom of the catholyte compartment 212.
Alternatively, the flow may be reversed, so that the flow is in the upward vertical direction. The solution may be fed at specific rates, such as in the range of 0.001 to 10 liters per minute or more depending on the electrochemical cell dimensions, so that the cathode gas diffusion electrode 204 may not be flooded with the catholyte solution due to excessive pressure, and so as to maintain good ionic contact with the cathode gas diffusion electrode 204 for the transfer of electrons into the solution in the reduction of carbon dioxide. The flow and pressure of the catholyte flow are such that minimal amounts of catholyte solution pass through the gas diffusion electrode 204 into the carbon dioxide gas plenum 206 inside the cathode current collector 208, and that the carbon dioxide gas reduction within the gas diffusion electrode is sufficient, so as to obtain a reasonable cathode current density, e.g. in the range of 10 mA/cm2 to 1000 mA/cm2, or more preferably in a range of about 50 to 500 mA/cm2. An energy source (not shown) is operably coupled with the electrodes 202 and 204 to reduce carbon dioxide at the cathode 204.
Carbon dioxide is fed to the gas-diffusion electrode 204 via entry 218 into the gas plenum 206.
Micro-channels 220 may be provided to pass carbon dioxide from the plenum 206 to the gas-diffusion electrode 204 that comprises the bismuth indium catalyst system.
Carbon dioxide leaves the cell through exit 222.
The anode side of the cell is similarly constructed. In this embodiment hydrogen gas is fed via entry 224 to gas plenum 226 provided with nnicrochannels 228 and leaves the cell via exit 230.
Anolyte is introduced at entry 232, flows through a distributor 234 down to the exit 236. A ion exchange membrane 238 is arranged between the anolyte and catholyte distributors 234 and 210.
The cathode trickle bed 210 may include a thin construction, e.g. made from non-conductive corrosion resistant polymer plastics, such as PTFE, polypropylene and the like, in the form of .. screen-like or convoluted forms so to distribute the catholyte solution evenly as it passes down the gas-diffusion electrode 204. Alternatively, the trickle bed material may include conductive carbon and graphite, or potentially be manufactured from metal. The entry and exit ports of the catholyte compartment are designed such that the flow distribution of liquid is uniform along the cross section of the trickle bed at the top and bottom. In another embodiment the GDE cathode .. may be able to be operated in a partially flooded or possibly fully flooded condition, and the flow conditions and electrolyte may be adjusted to operate the cathode in this mode.
Alternatively, the flow may be reversed, so that the flow is in the upward vertical direction. The solution may be fed at specific rates, such as in the range of 0.001 to 10 liters per minute or more depending on the electrochemical cell dimensions, so that the cathode gas diffusion electrode 204 may not be flooded with the catholyte solution due to excessive pressure, and so as to maintain good ionic contact with the cathode gas diffusion electrode 204 for the transfer of electrons into the solution in the reduction of carbon dioxide. The flow and pressure of the catholyte flow are such that minimal amounts of catholyte solution pass through the gas diffusion electrode 204 into the carbon dioxide gas plenum 206 inside the cathode current collector 208, and that the carbon dioxide gas reduction within the gas diffusion electrode is sufficient, so as to obtain a reasonable cathode current density, e.g. in the range of 10 mA/cm2 to 1000 mA/cm2, or more preferably in a range of about 50 to 500 mA/cm2. An energy source (not shown) is operably coupled with the electrodes 202 and 204 to reduce carbon dioxide at the cathode 204.
Carbon dioxide is fed to the gas-diffusion electrode 204 via entry 218 into the gas plenum 206.
Micro-channels 220 may be provided to pass carbon dioxide from the plenum 206 to the gas-diffusion electrode 204 that comprises the bismuth indium catalyst system.
Carbon dioxide leaves the cell through exit 222.
The anode side of the cell is similarly constructed. In this embodiment hydrogen gas is fed via entry 224 to gas plenum 226 provided with nnicrochannels 228 and leaves the cell via exit 230.
Anolyte is introduced at entry 232, flows through a distributor 234 down to the exit 236. A ion exchange membrane 238 is arranged between the anolyte and catholyte distributors 234 and 210.
The cathode trickle bed 210 may include a thin construction, e.g. made from non-conductive corrosion resistant polymer plastics, such as PTFE, polypropylene and the like, in the form of .. screen-like or convoluted forms so to distribute the catholyte solution evenly as it passes down the gas-diffusion electrode 204. Alternatively, the trickle bed material may include conductive carbon and graphite, or potentially be manufactured from metal. The entry and exit ports of the catholyte compartment are designed such that the flow distribution of liquid is uniform along the cross section of the trickle bed at the top and bottom. In another embodiment the GDE cathode .. may be able to be operated in a partially flooded or possibly fully flooded condition, and the flow conditions and electrolyte may be adjusted to operate the cathode in this mode.
9 Example 1 Screening catalyst Various binary metal catalysts were screened for their formate Faradaic yield in a test set up.
The test set up comprised a 3 chambered glass cell wherein the electrodes were positioned.
0.75M KHCO3 was used as elektrolyt. Potentiostatic (xV vs SCE) electrolysis for the electrochemical reduction of CO2 to formate was performed during 3.5-5 hrs.
Tables 1 and 2 show the results. It has appeared that a 50 wt.% Bi sample showed the best results in this screening test, while a 10 wt.% Bi sample outperformed a 90 wt.% Bi sample.
Table 1. Screening test results Catalyst E1/2 (V) vs SCE) Formate Faradaic Yield (cY0) In/Bi 50/50 -1.90 79.88 In/Bi 90/10 -1.90 76.81 Anodized In -1.75 75.73 In/Bi 10/90 -1.90 71.97 Bi/Pb 55.5/44.5 -1.90 70.87 Sn/Zn 60/40 -1.90 57.81 In/Sn 70/30 -1.90 53.64 In/Zn 90/10 -1.90 51.81 Sn/Pb 50/50 -1.90 48.42 In/Sn 30/70 -1.90 45.00 In/Sn 50/50 -1.90 41.46 In/Sn 30/70 -1.60 30.24 In/Sn 96/4 -1.75 28.79 Au/Ni (82/18) -1.90 3.35 In -1.9 63.47 Table 2. Screening Test Results Alloy E1/2 (V) vs SCE Formate Faradaic Yield (%) In/Sn 50:50 rod -1.46 7.69 -1.60 16.91 -1.90 54.21 Sn/Zn 60/40 -1.90 57.81 Bi:Pb -1.60 18.25 -1.75 68.78 -1.90 70.87 Sn:Pb -1.75 41.97 -1.90 48.42 In/Sn 70/30 -1.60 19.39 -1.75 46.87 -1.90 53.64 In/Sn 30/70 -1.60 30.24 -1.75 51.88 -1.90 45.00 In/Sn 96/4 -1.60 27.28 -1.75 28.79 In/Sn 50/50 -1.90 41.46 In/Bi 90/10 -1.75 82.26 -1.80 68.83 -1.90 76.82 In/Bi 10/90 -1.75 57.53 -1.80 65.57 -1.90 71.97 In/Bi 50/50 -1.75 73.70 -1.80 82.13 -1.90 79.88 In/Zn 90/10 -1.70 52.30 -1.80 59.64 -1.90 51.81 Example 2. Preparation of binary metal catalyst system In/Bi on C
InCI3, Bi(NO3)3*5H20 and tri-sodium citrate dehydrate were weighted as shown in Table 3 and put inside a two-neck round bottom flask containing 100 mL of tri-ethylene glycol and Vulcan carbon (available from Cabot). The round bottom flask was placed in an oil bath and fitted with a condenser. The system was continuously purged with N2 gas. The oil bath temperature was set to 100 C. The content of the flask was stirred. After the system reached the desired value of the temperature, it was allowed to stabilize for about 10 minutes, before rapidly injecting a water solution of NaBH4 using a syringe and needle. The NaBH4 was freshly prepared and sonicated in order to speed up the solubilization process. As soon as the NaBH4 was injected, a vigorous bubbling was observed in the mixture. The color of the suspension was black and no change in it was observed throughout the course of the reaction. After injecting NaBH4, the system was maintained at 100 C under stirring for 15 minutes. Then the heater was turned off and the suspension was allowed to cool slowly. At room temperature the suspension was transferred into 4 centrifuge tubes and centrifuged at 8000 rpm for 30 min. The supernatant was poured out and ethanol was added into the tubes, followed by a thorough washing. The washing was performed by sonicating the suspension for 10 min. Then centrifugation at 8000 rpm for 30 minutes was performed. This process was repeated 3 times. At the end ethanol (90 mL) was added into the tubes and the overall content was transferred in a 100 mL glass jar. The resulting mixture was sonicated for 40 minutes at room temperature and then magnetically stirred for 15 minutes. The thus obtained emulsion (catalyst ink) was ready for spray application.
The In:Bi weight ratio in the thus prepared catalyst is 52.3:47.6.
Table 3 Material Mass (mg) InCI3 310 BiNO3 x H20 340 Na3Citrate 441 Carbon 716 NaBH4 946 Example 3. Preparation of Gas Diffusion Electrode (GDE) A gas-diffusion electrode with a geometric surface area of about 172 cm2 was cut using a metallic blade. The GDE thus prepared was fixed on an aluminum panel using magnets and positioned at an angle of about 60 from the horizontal planed inside a ventilated fume hood.
The catalyst ink was sprayed on the GDE using a manual air brusher at room temperature under atmospheric conditions.
1.13
The test set up comprised a 3 chambered glass cell wherein the electrodes were positioned.
0.75M KHCO3 was used as elektrolyt. Potentiostatic (xV vs SCE) electrolysis for the electrochemical reduction of CO2 to formate was performed during 3.5-5 hrs.
Tables 1 and 2 show the results. It has appeared that a 50 wt.% Bi sample showed the best results in this screening test, while a 10 wt.% Bi sample outperformed a 90 wt.% Bi sample.
Table 1. Screening test results Catalyst E1/2 (V) vs SCE) Formate Faradaic Yield (cY0) In/Bi 50/50 -1.90 79.88 In/Bi 90/10 -1.90 76.81 Anodized In -1.75 75.73 In/Bi 10/90 -1.90 71.97 Bi/Pb 55.5/44.5 -1.90 70.87 Sn/Zn 60/40 -1.90 57.81 In/Sn 70/30 -1.90 53.64 In/Zn 90/10 -1.90 51.81 Sn/Pb 50/50 -1.90 48.42 In/Sn 30/70 -1.90 45.00 In/Sn 50/50 -1.90 41.46 In/Sn 30/70 -1.60 30.24 In/Sn 96/4 -1.75 28.79 Au/Ni (82/18) -1.90 3.35 In -1.9 63.47 Table 2. Screening Test Results Alloy E1/2 (V) vs SCE Formate Faradaic Yield (%) In/Sn 50:50 rod -1.46 7.69 -1.60 16.91 -1.90 54.21 Sn/Zn 60/40 -1.90 57.81 Bi:Pb -1.60 18.25 -1.75 68.78 -1.90 70.87 Sn:Pb -1.75 41.97 -1.90 48.42 In/Sn 70/30 -1.60 19.39 -1.75 46.87 -1.90 53.64 In/Sn 30/70 -1.60 30.24 -1.75 51.88 -1.90 45.00 In/Sn 96/4 -1.60 27.28 -1.75 28.79 In/Sn 50/50 -1.90 41.46 In/Bi 90/10 -1.75 82.26 -1.80 68.83 -1.90 76.82 In/Bi 10/90 -1.75 57.53 -1.80 65.57 -1.90 71.97 In/Bi 50/50 -1.75 73.70 -1.80 82.13 -1.90 79.88 In/Zn 90/10 -1.70 52.30 -1.80 59.64 -1.90 51.81 Example 2. Preparation of binary metal catalyst system In/Bi on C
InCI3, Bi(NO3)3*5H20 and tri-sodium citrate dehydrate were weighted as shown in Table 3 and put inside a two-neck round bottom flask containing 100 mL of tri-ethylene glycol and Vulcan carbon (available from Cabot). The round bottom flask was placed in an oil bath and fitted with a condenser. The system was continuously purged with N2 gas. The oil bath temperature was set to 100 C. The content of the flask was stirred. After the system reached the desired value of the temperature, it was allowed to stabilize for about 10 minutes, before rapidly injecting a water solution of NaBH4 using a syringe and needle. The NaBH4 was freshly prepared and sonicated in order to speed up the solubilization process. As soon as the NaBH4 was injected, a vigorous bubbling was observed in the mixture. The color of the suspension was black and no change in it was observed throughout the course of the reaction. After injecting NaBH4, the system was maintained at 100 C under stirring for 15 minutes. Then the heater was turned off and the suspension was allowed to cool slowly. At room temperature the suspension was transferred into 4 centrifuge tubes and centrifuged at 8000 rpm for 30 min. The supernatant was poured out and ethanol was added into the tubes, followed by a thorough washing. The washing was performed by sonicating the suspension for 10 min. Then centrifugation at 8000 rpm for 30 minutes was performed. This process was repeated 3 times. At the end ethanol (90 mL) was added into the tubes and the overall content was transferred in a 100 mL glass jar. The resulting mixture was sonicated for 40 minutes at room temperature and then magnetically stirred for 15 minutes. The thus obtained emulsion (catalyst ink) was ready for spray application.
The In:Bi weight ratio in the thus prepared catalyst is 52.3:47.6.
Table 3 Material Mass (mg) InCI3 310 BiNO3 x H20 340 Na3Citrate 441 Carbon 716 NaBH4 946 Example 3. Preparation of Gas Diffusion Electrode (GDE) A gas-diffusion electrode with a geometric surface area of about 172 cm2 was cut using a metallic blade. The GDE thus prepared was fixed on an aluminum panel using magnets and positioned at an angle of about 60 from the horizontal planed inside a ventilated fume hood.
The catalyst ink was sprayed on the GDE using a manual air brusher at room temperature under atmospheric conditions.
1.13
Claims (15)
1. Catalyst system for catalyzed electrochemical reactions, comprising a catalyst, wherein the catalyst comprises 5-94 wt.% bismuth and 6-95 wt.% indium, based on the total amount of bismuth and indium.
2. Catalyst system according to claim 1, comprising an electrically conductive support and a catalyst, wherein the catalyst comprises 5-94 wt.% bismuth and 6-95 wt.%
indium, based on the total amount of bismuth and indium.
indium, based on the total amount of bismuth and indium.
3. Catalyst system according to claim 1 or 2, wherein the amount of bismuth is in the range of 10-90 wt.%, based on the total amount of bismuth and indium.
4. Catalyst system according to any one of claims 1 to 3, wherein the amount of bismuth is in the range of 40-60 wt.%, based on the total amount of bismuth and indium
5. Catalyst system according to claim 2, wherein the conductive support comprises a porous structure of carbon particles.
6. Gas-diffusion electrode comprising a gas-diffusion layer on a conductive substrate, the gas-diffusion layer comprising the catalyst system according to any one of the preceding claims.
7. Gas-diffusion electrode according to claim 6, wherein the catalyst system is bonded to the conductive substrate by a hydrophobic binder.
8. Electrochemical cell comprising at least one gas chamber and at least one liquid chamber, which chambers are separated by a gas-diffusion electrode according to any one of claims 6 to 7.
9. Method of preparing a gas-diffusion electrode according to any one of claims 6 to 7, comprising a catalyst system according to any one of claims 1 to 5, the method comprising the steps of providing a conductive substrate;
applying bismuth, indium, conductive support and a binder to the conductive substrate.
applying bismuth, indium, conductive support and a binder to the conductive substrate.
10. Method according to claim 9, wherein the binder is a hydrophobic binder.
11. Method of electrocatalytically reducing carbon dioxide, comprising 5 introducing an anolyte to a first cell compartment of an electrochemical cell, the first cell compartment comprising an anode;
introducing a catholyte and carbon dioxide to a second cell compartment of the electrochemical cell, the second cell compartment comprising a cathode, and applying an electrical potential between the anode and the cathode sufficient to reduce the 10 carbon dioxide to a reduced reaction product, wherein the cathode comprises a catalyst system according to any one of claims 1 to 5.
introducing a catholyte and carbon dioxide to a second cell compartment of the electrochemical cell, the second cell compartment comprising a cathode, and applying an electrical potential between the anode and the cathode sufficient to reduce the 10 carbon dioxide to a reduced reaction product, wherein the cathode comprises a catalyst system according to any one of claims 1 to 5.
12. Method according to claim 11, wherein the cathode is a gas-diffusion electrode according to any one of claims 6 to 7.
13. Method according to claim 11 or 12, wherein carbon dioxide is reduced to a reaction product selected from carboxylates and carboxylic acids.
14. Method according to any one of claims 11 to 13, wherein carbon dioxide is reduced to formate or formic acid in an aqueous medium.
15. Method according to any one of claims 11 to 13, wherein carbon dioxide is reduced to oxalate or oxalic acid in a non-aqueous medium.
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