JP6059140B2 - 電気化学セル - Google Patents
電気化学セル Download PDFInfo
- Publication number
- JP6059140B2 JP6059140B2 JP2013518759A JP2013518759A JP6059140B2 JP 6059140 B2 JP6059140 B2 JP 6059140B2 JP 2013518759 A JP2013518759 A JP 2013518759A JP 2013518759 A JP2013518759 A JP 2013518759A JP 6059140 B2 JP6059140 B2 JP 6059140B2
- Authority
- JP
- Japan
- Prior art keywords
- hydrogen
- reaction
- catalyst
- choline
- cocatalyst
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- 238000006243 chemical reaction Methods 0.000 claims description 177
- 239000001257 hydrogen Substances 0.000 claims description 111
- 229910052739 hydrogen Inorganic materials 0.000 claims description 111
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 110
- 229910052763 palladium Inorganic materials 0.000 claims description 34
- 229910052697 platinum Inorganic materials 0.000 claims description 31
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 30
- 229910052759 nickel Inorganic materials 0.000 claims description 16
- 229910052718 tin Inorganic materials 0.000 claims description 16
- 239000001569 carbon dioxide Substances 0.000 claims description 15
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 15
- 239000003112 inhibitor Substances 0.000 claims description 13
- 150000001768 cations Chemical class 0.000 claims description 12
- 229960001231 choline Drugs 0.000 claims description 11
- 229910052804 chromium Inorganic materials 0.000 claims description 11
- 150000003248 quinolines Chemical class 0.000 claims description 11
- 229910052707 ruthenium Inorganic materials 0.000 claims description 11
- 229910052709 silver Inorganic materials 0.000 claims description 11
- 229910052793 cadmium Inorganic materials 0.000 claims description 10
- OEYIOHPDSNJKLS-UHFFFAOYSA-N choline Chemical compound C[N+](C)(C)CCO OEYIOHPDSNJKLS-UHFFFAOYSA-N 0.000 claims description 10
- 229910052802 copper Inorganic materials 0.000 claims description 10
- 229910052710 silicon Inorganic materials 0.000 claims description 10
- 229910052787 antimony Inorganic materials 0.000 claims description 9
- 229910052797 bismuth Inorganic materials 0.000 claims description 9
- 229910052742 iron Inorganic materials 0.000 claims description 9
- 229910052745 lead Inorganic materials 0.000 claims description 9
- 229910052721 tungsten Inorganic materials 0.000 claims description 9
- 229910052726 zirconium Inorganic materials 0.000 claims description 9
- 229910052684 Cerium Inorganic materials 0.000 claims description 8
- 229910052772 Samarium Inorganic materials 0.000 claims description 8
- 229910052771 Terbium Inorganic materials 0.000 claims description 8
- 239000012530 fluid Substances 0.000 claims description 8
- 229910052735 hafnium Inorganic materials 0.000 claims description 8
- 229910052738 indium Inorganic materials 0.000 claims description 8
- 229910052741 iridium Inorganic materials 0.000 claims description 8
- 229910052746 lanthanum Inorganic materials 0.000 claims description 8
- 229910052748 manganese Inorganic materials 0.000 claims description 8
- 229910052750 molybdenum Inorganic materials 0.000 claims description 8
- 229910052758 niobium Inorganic materials 0.000 claims description 8
- 229910052702 rhenium Inorganic materials 0.000 claims description 8
- 229910052703 rhodium Inorganic materials 0.000 claims description 8
- 229910052715 tantalum Inorganic materials 0.000 claims description 8
- 229910052716 thallium Inorganic materials 0.000 claims description 8
- 229910052720 vanadium Inorganic materials 0.000 claims description 8
- 229910052779 Neodymium Inorganic materials 0.000 claims description 7
- 239000007795 chemical reaction product Substances 0.000 claims description 6
- 239000007864 aqueous solution Substances 0.000 claims description 5
- 229910052799 carbon Inorganic materials 0.000 claims description 5
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 3
- 125000000896 monocarboxylic acid group Chemical group 0.000 claims 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 155
- 229910002091 carbon monoxide Inorganic materials 0.000 description 155
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 106
- 239000003054 catalyst Substances 0.000 description 73
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 63
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 63
- 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 53
- 235000019253 formic acid Nutrition 0.000 description 53
- 239000000203 mixture Substances 0.000 description 53
- 239000001763 2-hydroxyethyl(trimethyl)azanium Substances 0.000 description 49
- 229960003178 choline chloride Drugs 0.000 description 49
- 235000019743 Choline chloride Nutrition 0.000 description 45
- SGMZJAMFUVOLNK-UHFFFAOYSA-M choline chloride Chemical compound [Cl-].C[N+](C)(C)CCO SGMZJAMFUVOLNK-UHFFFAOYSA-M 0.000 description 45
- 238000000034 method Methods 0.000 description 43
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 32
- 239000003792 electrolyte Substances 0.000 description 31
- 229910052737 gold Inorganic materials 0.000 description 31
- 239000010931 gold Substances 0.000 description 31
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 30
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 25
- 239000000243 solution Substances 0.000 description 24
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 23
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 22
- 239000000446 fuel Substances 0.000 description 21
- 230000000694 effects Effects 0.000 description 20
- 238000002474 experimental method Methods 0.000 description 20
- 239000000543 intermediate Substances 0.000 description 19
- 230000008569 process Effects 0.000 description 19
- 239000000047 product Substances 0.000 description 18
- -1 carboxylic acid ions Chemical class 0.000 description 17
- 238000002484 cyclic voltammetry Methods 0.000 description 16
- 229910052751 metal Inorganic materials 0.000 description 16
- 239000002184 metal Substances 0.000 description 16
- 238000006722 reduction reaction Methods 0.000 description 16
- 238000012552 review Methods 0.000 description 16
- 239000000126 substance Substances 0.000 description 15
- 239000011135 tin Substances 0.000 description 15
- 238000005259 measurement Methods 0.000 description 14
- 230000009467 reduction Effects 0.000 description 14
- 230000015572 biosynthetic process Effects 0.000 description 13
- 125000004122 cyclic group Chemical group 0.000 description 13
- 238000006056 electrooxidation reaction Methods 0.000 description 13
- 150000003839 salts Chemical class 0.000 description 13
- 230000001629 suppression Effects 0.000 description 13
- 239000000463 material Substances 0.000 description 12
- 239000000376 reactant Substances 0.000 description 12
- 238000001179 sorption measurement Methods 0.000 description 12
- 150000001412 amines Chemical group 0.000 description 11
- 229910052786 argon Inorganic materials 0.000 description 11
- 238000006555 catalytic reaction Methods 0.000 description 11
- 239000002904 solvent Substances 0.000 description 11
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 10
- 239000011651 chromium Substances 0.000 description 10
- 150000002500 ions Chemical class 0.000 description 10
- 238000004519 manufacturing process Methods 0.000 description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- 238000007086 side reaction Methods 0.000 description 10
- FNPBHXSBDADRBT-UHFFFAOYSA-M 2-hydroxyethyl(trimethyl)azanium;iodide Chemical compound [I-].C[N+](C)(C)CCO FNPBHXSBDADRBT-UHFFFAOYSA-M 0.000 description 9
- 239000003426 co-catalyst Substances 0.000 description 9
- 239000010949 copper Substances 0.000 description 9
- 230000006870 function Effects 0.000 description 9
- 239000002608 ionic liquid Substances 0.000 description 9
- 230000002829 reductive effect Effects 0.000 description 9
- 238000012360 testing method Methods 0.000 description 9
- 150000004820 halides Chemical class 0.000 description 8
- 150000002431 hydrogen Chemical class 0.000 description 8
- 238000003795 desorption Methods 0.000 description 7
- 229910052753 mercury Inorganic materials 0.000 description 7
- 239000012071 phase Substances 0.000 description 7
- 230000002441 reversible effect Effects 0.000 description 7
- 239000004381 Choline salt Substances 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 229910021607 Silver chloride Inorganic materials 0.000 description 6
- 239000002253 acid Substances 0.000 description 6
- 229910052782 aluminium Inorganic materials 0.000 description 6
- 150000001450 anions Chemical class 0.000 description 6
- 239000000460 chlorine Substances 0.000 description 6
- 235000019417 choline salt Nutrition 0.000 description 6
- 238000000970 chrono-amperometry Methods 0.000 description 6
- 230000005518 electrochemistry Effects 0.000 description 6
- 238000005868 electrolysis reaction Methods 0.000 description 6
- SHFJWMWCIHQNCP-UHFFFAOYSA-M hydron;tetrabutylazanium;sulfate Chemical compound OS([O-])(=O)=O.CCCC[N+](CCCC)(CCCC)CCCC SHFJWMWCIHQNCP-UHFFFAOYSA-M 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 6
- OIPILFWXSMYKGL-UHFFFAOYSA-N acetylcholine Chemical compound CC(=O)OCC[N+](C)(C)C OIPILFWXSMYKGL-UHFFFAOYSA-N 0.000 description 5
- 239000000654 additive Substances 0.000 description 5
- 230000008901 benefit Effects 0.000 description 5
- 239000007853 buffer solution Substances 0.000 description 5
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 5
- 238000010586 diagram Methods 0.000 description 5
- 239000011521 glass Substances 0.000 description 5
- 238000007254 oxidation reaction Methods 0.000 description 5
- 125000005496 phosphonium group Chemical group 0.000 description 5
- 235000017557 sodium bicarbonate Nutrition 0.000 description 5
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 5
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 4
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 4
- 230000000996 additive effect Effects 0.000 description 4
- 230000002411 adverse Effects 0.000 description 4
- 125000003277 amino group Chemical group 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 238000003487 electrochemical reaction Methods 0.000 description 4
- 230000005496 eutectics Effects 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 230000002401 inhibitory effect Effects 0.000 description 4
- 230000003993 interaction Effects 0.000 description 4
- 125000005647 linker group Chemical group 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 239000013580 millipore water Substances 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 230000006641 stabilisation Effects 0.000 description 4
- 238000011105 stabilization Methods 0.000 description 4
- KYCQOKLOSUBEJK-UHFFFAOYSA-M 1-butyl-3-methylimidazol-3-ium;bromide Chemical compound [Br-].CCCCN1C=C[N+](C)=C1 KYCQOKLOSUBEJK-UHFFFAOYSA-M 0.000 description 3
- WHBHBVVOGNECLV-OBQKJFGGSA-N 11-deoxycortisol Chemical compound O=C1CC[C@]2(C)[C@H]3CC[C@](C)([C@@](CC4)(O)C(=O)CO)[C@@H]4[C@@H]3CCC2=C1 WHBHBVVOGNECLV-OBQKJFGGSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 3
- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical compound [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 125000001931 aliphatic group Chemical group 0.000 description 3
- 229910021538 borax Inorganic materials 0.000 description 3
- 230000005587 bubbling Effects 0.000 description 3
- 239000000872 buffer Substances 0.000 description 3
- 125000002843 carboxylic acid group Chemical group 0.000 description 3
- 150000001735 carboxylic acids Chemical class 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 229910052801 chlorine Inorganic materials 0.000 description 3
- 230000005611 electricity Effects 0.000 description 3
- 239000011737 fluorine Substances 0.000 description 3
- 229910052731 fluorine Inorganic materials 0.000 description 3
- 238000005984 hydrogenation reaction Methods 0.000 description 3
- 239000003446 ligand Substances 0.000 description 3
- 230000007246 mechanism Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 125000004433 nitrogen atom Chemical group N* 0.000 description 3
- 125000004437 phosphorous atom Chemical group 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M potassium hydroxide Substances [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 239000004332 silver Substances 0.000 description 3
- 239000004328 sodium tetraborate Substances 0.000 description 3
- 235000010339 sodium tetraborate Nutrition 0.000 description 3
- CSPHGSFZFWKVDL-UHFFFAOYSA-M (3-chloro-2-hydroxypropyl)-trimethylazanium;chloride Chemical compound [Cl-].C[N+](C)(C)CC(O)CCl CSPHGSFZFWKVDL-UHFFFAOYSA-M 0.000 description 2
- IQQRAVYLUAZUGX-UHFFFAOYSA-N 1-butyl-3-methylimidazolium Chemical compound CCCCN1C=C[N+](C)=C1 IQQRAVYLUAZUGX-UHFFFAOYSA-N 0.000 description 2
- VCOBYGVZILHVOO-UHFFFAOYSA-M 2-butanoyloxyethyl(trimethyl)azanium;chloride Chemical compound [Cl-].CCCC(=O)OCC[N+](C)(C)C VCOBYGVZILHVOO-UHFFFAOYSA-M 0.000 description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-M Formate Chemical compound [O-]C=O BDAGIHXWWSANSR-UHFFFAOYSA-M 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O ammonium group Chemical group [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 2
- 239000003125 aqueous solvent Substances 0.000 description 2
- 238000004364 calculation method Methods 0.000 description 2
- 150000007942 carboxylates Chemical group 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000002848 electrochemical method Methods 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 239000011888 foil Substances 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- LPPJNZJBKFSQGA-UHFFFAOYSA-M hydron;2-hydroxyethyl(trimethyl)azanium;phosphate Chemical compound OP(O)([O-])=O.C[N+](C)(C)CCO LPPJNZJBKFSQGA-UHFFFAOYSA-M 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 230000005764 inhibitory process Effects 0.000 description 2
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- TZIHFWKZFHZASV-UHFFFAOYSA-N methyl formate Chemical compound COC=O TZIHFWKZFHZASV-UHFFFAOYSA-N 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
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- 239000002245 particle Substances 0.000 description 2
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- 229940112042 peripherally acting choline derivative muscle relaxants Drugs 0.000 description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
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- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 2
- 241000894007 species Species 0.000 description 2
- 238000004611 spectroscopical analysis Methods 0.000 description 2
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- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid Chemical compound OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 2
- RWSOTUBLDIXVET-UHFFFAOYSA-O sulfonium Chemical compound [SH3+] RWSOTUBLDIXVET-UHFFFAOYSA-O 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- KXCVJPJCRAEILX-UHFFFAOYSA-M 1-butyl-3-methylimidazol-3-ium;hydrogen sulfate Chemical compound OS([O-])(=O)=O.CCCCN1C=C[N+](C)=C1 KXCVJPJCRAEILX-UHFFFAOYSA-M 0.000 description 1
- CWLUFVAFWWNXJZ-UHFFFAOYSA-N 1-hydroxypyrrolidine Chemical compound ON1CCCC1 CWLUFVAFWWNXJZ-UHFFFAOYSA-N 0.000 description 1
- KJJPLEZQSCZCKE-UHFFFAOYSA-N 2-aminopropane-1,3-diol Chemical compound OCC(N)CO KJJPLEZQSCZCKE-UHFFFAOYSA-N 0.000 description 1
- 125000001340 2-chloroethyl group Chemical group [H]C([H])(Cl)C([H])([H])* 0.000 description 1
- JJCWKVUUIFLXNZ-UHFFFAOYSA-M 2-hydroxyethyl(trimethyl)azanium;bromide Chemical compound [Br-].C[N+](C)(C)CCO JJCWKVUUIFLXNZ-UHFFFAOYSA-M 0.000 description 1
- FHCUSSBEGLCCHQ-UHFFFAOYSA-M 2-hydroxyethyl(trimethyl)azanium;fluoride Chemical compound [F-].C[N+](C)(C)CCO FHCUSSBEGLCCHQ-UHFFFAOYSA-M 0.000 description 1
- WWILHZQYNPQALT-UHFFFAOYSA-N 2-methyl-2-morpholin-4-ylpropanal Chemical compound O=CC(C)(C)N1CCOCC1 WWILHZQYNPQALT-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- 239000004475 Arginine Substances 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- 239000002000 Electrolyte additive Substances 0.000 description 1
- RAXXELZNTBOGNW-UHFFFAOYSA-O Imidazolium Chemical compound C1=C[NH+]=CN1 RAXXELZNTBOGNW-UHFFFAOYSA-O 0.000 description 1
- 238000003109 Karl Fischer titration Methods 0.000 description 1
- QNAYBMKLOCPYGJ-REOHCLBHSA-N L-alanine Chemical compound C[C@H](N)C(O)=O QNAYBMKLOCPYGJ-REOHCLBHSA-N 0.000 description 1
- ODKSFYDXXFIFQN-BYPYZUCNSA-P L-argininium(2+) Chemical compound NC(=[NH2+])NCCC[C@H]([NH3+])C(O)=O ODKSFYDXXFIFQN-BYPYZUCNSA-P 0.000 description 1
- CKLJMWTZIZZHCS-REOHCLBHSA-N L-aspartic acid Chemical compound OC(=O)[C@@H](N)CC(O)=O CKLJMWTZIZZHCS-REOHCLBHSA-N 0.000 description 1
- AYFVYJQAPQTCCC-GBXIJSLDSA-N L-threonine Chemical compound C[C@@H](O)[C@H](N)C(O)=O AYFVYJQAPQTCCC-GBXIJSLDSA-N 0.000 description 1
- BAVYZALUXZFZLV-UHFFFAOYSA-O Methylammonium ion Chemical compound [NH3+]C BAVYZALUXZFZLV-UHFFFAOYSA-O 0.000 description 1
- 229920000557 Nafion® Polymers 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 238000001069 Raman spectroscopy Methods 0.000 description 1
- 229910017835 Sb—Sn Inorganic materials 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- AYFVYJQAPQTCCC-UHFFFAOYSA-N Threonine Natural products CC(O)C(N)C(O)=O AYFVYJQAPQTCCC-UHFFFAOYSA-N 0.000 description 1
- 239000004473 Threonine Substances 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 150000001242 acetic acid derivatives Chemical class 0.000 description 1
- 229960004373 acetylcholine Drugs 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000002156 adsorbate Substances 0.000 description 1
- 235000004279 alanine Nutrition 0.000 description 1
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Images
Classifications
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Description
この出願は、2011年6月30日に出願された仮出願ではない米国特許出願番号13/174,365号(発明の名称「Novel Catalyst Mixtures」)に関連し、かつ優先権の利益を請求する。また、この出願は、2011年5月9日に出願された米国特許仮出願番号61/484,072号(発明の名称「Novel Catalyst Mixtures」)、2010年7月4日に出願された仮出願ではない米国特許出願番号12/830,338号(発明の名称「Novel Catalyst Mixtures」)、及び2011年3月25日に出願された国際特許出願番号PCT/US2011/30098号(発明の名称「Novel Catalyst Mixtures」)に関連し、かつ優先権の利益を請求する。‘365出願、‘072出願、‘338出願、及び‘098出願のそれぞれが、参照により完全に本明細書に組み込まれる。
本明細書において用語「CO2の電気化学的転換」は、電気化学的プロセスの任意の工程で、二酸化炭素、炭酸塩、又は重炭酸塩が別の化学物質に転換されるプロセスを意味する。
(a)標準的な3電極電気化学セルに、反応Rに一般的に使用されている電解質を満たす。一般的な電解質には、0.1Mの硫酸があり、又は0.1MのKOH水溶液も使用することができる。
(b)活性金属を、3電極電気化学セルと適切な対電極に取り付ける。
(c)数回のCVサイクルを実行して、活性金属を洗浄する。
(d)電解質中の可逆水素電極(RHE)電位を測定する。
(e)反応Rの反応物をセルに充填し、反応Rに関連するピークの電位に注意しながら、反応RのCVを測定する。
(f)V1=RHEと反応に関連するピークの開始電位の差を計算する。
(g)V1A=RHEと反応に関連するピークの最大電位の差を計算する。
(h)0.0001〜99.9999%の物質Sを電解質に加える。
(i)助触媒を用いる反応におけるRHEを測定する。
(j)反応Rに関連するピークの電位に注意しながら、反応RのCVを再度測定する。
(k)V2=RHEと反応に関連するピークの開始電位の差を計算する。
(l)V2A=RHEと反応に関連するピークの最大電位の差を計算する。
以下では、上で引用した関連出願で開示されている活性元素−助触媒混合物に対して用いた試験手順を記載する。これらの特定の実験では、CO2の電気化学的転換の過電圧を低下させ、かつ反応の選択率(電流効率)を向上させるための、白金及び1−エチル−3−メチルイミダゾリウムテトラフルオロボラート(EMIM−BF4)からなる活性元素−助触媒混合物の性能を測定した。したがって、この試験は、EMIM−BF4及びEMIM+イオンがそれぞれ誘導分子及び誘導イオンとして所望の反応で機能できるかどうかを判断することができる。この試験における所望の反応は、(典型的には、一次生成物(primary product)、例えばCO又はギ酸への)二酸化炭素の電気化学的還元となるであろう。
この実験は、水の添加がCO形成速度を上昇させることを示す。この実験は、例1に記載のセルと手順を用いたが、以下の例外を含む:例1で使用した99.9999%のEMIM−BF4の代わりに、98.55%のEMIM−BF4と0.45%の水とを含む溶液を使用し、電位は、RHEに対して−0.6Vで10又は30分間維持し、次に電位を50mV/秒でプラスに上げた。図10にその結果を示す。1.2Vと5Vとの間のピークに注意されたい。これはCO形成に関連するピークであり、例1のものよりはるかに大きい。すなわち水の添加は、おそらく反応物として作用することによりCO形成を加速させた。
(パラジウム及びヨウ化コリンを含む活性元素−助触媒混合物の使用による、水中でのCO2の電気化学的転換に関する過電圧の低下並びに水素生成の抑制)
(パラジウム及び塩化コリンを含む活性元素−助触媒混合物の使用による、CO2のギ酸への電気化学的転換に関する過電圧の低下並びに水素生成の抑制)
(ニッケル及び塩化コリンを含む活性元素−助触媒混合物の使用による、CO2からCOへの電気化学的転換に関する過電圧の低下並びに水素生成の抑制)
(塩化コリンの存在下でのギ酸電気酸化の促進及び水素発生反応(HER)の抑制)
5.6mgのメタルブラック(Alfa Aesar 金属に基づいて99.9%)を、1mlの脱酸素Millipore水と混合することによって、触媒メタルブラックインクを調製した。2種類の対電極をこの実験で用いた。白金触媒及びパラジウム触媒に関して、25×25mmの白金メッシュ(サイズ52)を5インチの白金ワイヤ(99.9%、直径0.004インチ)に連結することによって、対電極を作製した。参照電極は、フレキシブルコネクタを有する銀−塩化銀電極であった。次の4種類の電解質を用いた:0.5Mの塩化コリン、0.5Mの重炭酸ナトリウム、0.5Mの硫酸及び緩衝液。この溶液を、三回蒸留した水で調製した。25℃で、アルゴンガス(99.999%の純度)をバブリングしながら、1atmで測定を行った。
Ag/AgCl参照電極を有する標準の三電極電解セルにおいて、Solartron SI 1287ポテンショスタットを用いて測定を行った。メタルブラックインクを回転電極の金属表面に適用することによって、作用電極を調製した。12.5μLのインクをその表面に添加し、60分間常温で水を揮発させることによって、回転電極の表面に触媒を適用した。
まず、電解質をガラスセルに装填し、そして電解質から酸素を除去するためにドライアルゴンで2時間パージした。各実験の前に、電極を調整し、表面から酸化物を除去するために、75mV/sで20〜40回のリニアスイープのサイクリックボルタモグラムを、Ag/AgClに対して−1.5V〜+1Vでとった。そして、最終のサイクルを行う前に、複数のサイクルを10mV/sで行って、CVの安定化を確実にした(すなわち、「汚れ」又は他の材料を表面から除去した)。最終的に、クリーニング及び安定化のCVサイクルを、10mV/sで行った。その後、ギ酸を電解質に添加し、その最終濃度を、0.001M、0.01M、及び0.03Mとした。CVを再び行って、ギ酸と触媒表面との反応を調査した。測定の質を確保するために、材料のクリーニングと溶液の純度に特に注意をした(Quaino,P.M.,Gennero De Chialvo, M.R.,及びChialvo, A.C., Hydrogen Diffusion Effects on the Kinetics of the Hydrogen Electrode Reaction Part II. Evaluation of Kinetic Parameters, Physical Chemistry Chemical Physics, 6(18):4450−4455ページ(2004年) 及びMontero, M.A., Marozzi, C.A., Chialvo, M.R.G.D., and Chialvo, A.C., The Evaluation of the Polarization Resistance in a Tubular Electrode and Its Application to the Hydrogen Electrode Reaction. Electrochimica Acta, 2007年. 52(5): 2083−2090ページを参照できる)。
まず、参照電極を安定化させるために、Luggin Capillaryを介してセルに連結したAg/AgCl参照電極を用いた。しかし、この参照電極は、塩化コリン混合物にさらした時に、ドリフトする場合があることが分かった。したがって、各実験中に参照電極を、可逆水素電極(RHE)に対して再較正した。本質的に、対電極に対して水素をバブリングすることによって、RHEを設定し、そしてこの電極の電位を参照電極と比較した。RHEの電位を測定するために、作用電極及び対電極のリード線をショートさせ、そして20分間、対電極の下で水素をバブリングさせた後、オープンセルの電位を、安定化するまで測定した。このオープンセルの電位は、RHE対Ag/AgCl電極であった。これは、各ランに関して参照電極の測定を可能にした。参照電極のドリフトに関する問題を回避するため、この作業に続いて、データを可逆水素電極の測定電位に対してプロットした。表4に示したように、4つの溶液を用いた。0.5Mの塩化コリン溶液を次の3つの標準溶液と比較した:0.5Mの重炭酸ナトリウム、0.5Mの硫酸及びホウ砂緩衝溶液。硫酸を内部標準とした。重炭酸ナトリウム及びホウ砂緩衝剤は、塩化コリン溶液と同様のpHを有しており、これらは良好な比較対象であった。
クロノアンペロメトリーを、オープンセル電位(open cell potential)から目的の電位まで変化させることで、特記しない限り、通常に測定した。クロノアンペロメトリーのデータに関して言及した電位は、オープンセルの電位から変化させた電位である。次の2種類の電解質を測定のために調製した:0.01Mのギ酸溶液、及び0.5Mの塩化コリン中の0.01Mのギ酸。RHEに対して0.2Vで電位を保持して、電流−時間(I−t)曲線をポテンショスタットを用いて記録した。
水素発生反応の抑制:
第一の実験では、塩化コリンがHERを阻害できるかどうかを判断した。サイクリックボルタンメトリーを各溶液について行って、水素発生反応がどのように変化するかを観察した。
上記の結果は、水素生成が塩化コリンの存在下で強く抑制されることを示した。対処すべき次の課題は、触媒が完全に劣化しているか、又は逆にギ酸の電気酸化に有利な影響があるのかどうかである。
他の1つの問題は、ギ酸の電気酸化が、塩化コリンの存在下で強まるかどうかである。図20は、0.01Mのギ酸を有する塩化コリン電解質について、RHEに対して0.2Vで行ったPtに関するクロノアンペロメトリースキャンを、純粋なギ酸電解質と比較して示す。ギ酸燃料電池で用いられる電位に近いため、0.2Vの電位を選択した。
他の作業で、本発明者らは、表面増感ラマン分光測定(SERS)を行って、金の膜への塩化コリンの吸着を試験した。全ての場合において、吸着したコリンカチオンに関して予測されるように、2976cm−1、1453cm−1、967cm−1、717cm−1で、大きなピークを観測した。したがって、予想されるように、コリンイオンが金に分子的に吸着するということが結論付けられた。
発明者らは、電気化学セルでの水素発生を抑制する等の目的のため、誘導分子(又はイオン)として用いるために、これらの化学物質種が、少なくとも1つの正荷電基、及び表面結合のための(例えば、陰極に結合するための)少なくとも1つの基を有する必要があると考えている。すなわち、必要なものは、表面に悪影響を与えるような強い結合ではなく、表面に正電荷を保持させるためのものを有する正荷電種である。多数のアルコール類、アルデヒド類、ケトン類、及びカルボン酸類が機能するはずだが、いくつかのカルボン酸は、電極表面に強すぎる結合をなす場合があり、そして所望の反応に悪影響を与えることがある。同様に、−OR、−COR、−COORに加えて他の極性基、例えば−NR2、−PR2、−SR及びハライド(ここで、R基は独立して、H又は炭素含有配位子となり;カルボン酸基及びそれらの塩は除かれる場合がある)は、表面結合基として十分に機能することがある。正荷電基に関して、様々なアミン及びホスホニウムが十分に機能するはずである。重要なことは、結合基を与えて、表面にそれらを結合させることであり、また正電荷基は、疎水性となるような大きさにならないべきである。メチル、エチル及びプロピルの第四級アミンが、良好に機能するはずである。結合基を有する場合、イミダゾリウム類(イミダゾニウムと呼ばれることもある)も十分に機能するはずである。本発明の有意な態様は、助触媒(所望の反応に関する過電圧を低下させる又は加速させる)と誘導分子(例えば、所望の反応より不必要な反応を強く阻害することによって、所望の反応に向けての選択率を向上させる)との両方で機能することができる分子又はイオンの同定である。
(活性元素(金)−助触媒混合物がCO2センサーに有用であることの証明)
このセンサーは、単純な電気化学的素子であってよく、ここでは活性元素−助触媒混合物が電気化学的素子のアノードとカソード上に位置し、そうしてこのセンサーの抵抗が測定されてもよい。CO2が存在しない場合は、抵抗が高くなるであろうが、リーク電流に起因して好ましくは無限大ではない。CO2が存在する場合は、活性元素−助触媒混合物がCO2の転換を触媒することができる。これは、より大きな電流をセンサーに流す。結果として、センサーの抵抗が低下する。その結果、センサーは、二酸化炭素を検出するのに用いることができる。
(一酸化炭素の定常状態での製造)
この実験では、Devin T.Whipple,E.C.Finke,and P.J.A. Kenis、Electrochem.& Solid−State Lett.、2010年、13(9)、B109−B111(Whipple論文)に記載のフローセルを使用した。第1の触媒インクを以下のように調製した:
(他のコリン誘導体を用いての水素抑制の証明)
この実験は、塩化コリンの代わりに、(a)酢酸コリン、(b)コリンBF4、(c)(3−クロロ−2−ヒドロキシプロピル)トリメチルアンモニウムクロリド、(d)ブチリルコリンクロリド、及び(e)(2−クロロエチル)トリメチルアンモニウムクロリドを用いたことを除いて(塩化コリンも比較のために示されている)、具体例4と同じである。図25a、25b、26a、26b、27a及び27bは、具体例2で記載されたように行ったCVを、白金触媒、パラジウム触媒、及び白金/ルテニウム触媒について示している。すべての場合に、水素の抑制が観察された。この結果は、(a)酢酸コリン、(b)コリンBF4、(c)(3−クロロ−2−ヒドロキシプロピル)トリメチルアンモニウムクロリド、(d)ブチリルコリンクロリド、及び(e)(2−クロロエチル)トリメチルアンモニウムクロリドの全てが水素抑制剤であることを示している。
Claims (3)
- 陽極、陰極及び水素発生抑制剤を含有する流動相を含む、二酸化炭素を少なくとも1つの反応生成物に転換するための電気化学セルであって、
前記水素発生抑制剤が、カチオンを有し、
前記カチオンが、次の式のコリン誘導体又はコリンであり:
R1R2R3N+(CH2)nY
(ここで、n=1〜4であり;R1R2及びR3は、C1〜C4脂肪族基、−CH2OH、−CH2CH2OH、−CH2CH2CH2OH、−CH2CHOHCH3からなる群より独立して選択され;かつYはヒドロキシルである)、
前記少なくとも1つの反応生成物が、CO、HCO−、H2CO、(HCO2)−、H2CO2、CH3OH、CH4、C2H4、CH3CH2OH、CH3COO−、CH3COOH、C2H6、(COOH)2、及び(COO−)2の少なくとも1つを含み、
前記陰極は、V、Cr、Mn、Fe、Co、Ni、Cu、Sn、Zr、Nb、Mo、Ru、Rh、Pd、Ag、Cd、Hf、Ta、W、Re、Ir、Pt、Au、Hg、Al、Si、C、In、Tl、Pb、Bi、Sb、Te、U、Sm、Tb、La、Ce及びNdの少なくとも1つとなることができる、触媒活性元素を含む、
電気化学セル。 - 前記水素発生抑制剤を含有する流動相が、前記陰極と接触している水溶液である、請求項1に記載の電気化学セル。
- 前記触媒活性元素及び前記水素発生抑制剤が、CO2の存在下で電気化学セルに電圧を印加した場合に、前記少なくとも1つの反応生成物へのCO2の転換の開始が、標準水素電極(SHE)に対して−0.9V以上であるカソード電位で始まる、請求項1に記載の電気化学セル。
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CN102971451A (zh) | 2013-03-13 |
CA2802893A1 (en) | 2012-01-12 |
JP2013538285A (ja) | 2013-10-10 |
KR101801659B1 (ko) | 2017-11-27 |
US20120308903A1 (en) | 2012-12-06 |
WO2012006240A4 (en) | 2012-02-02 |
CA2802893C (en) | 2018-08-28 |
KR20130043178A (ko) | 2013-04-29 |
JP6449839B2 (ja) | 2019-01-09 |
JP2017082334A (ja) | 2017-05-18 |
AU2011276362A1 (en) | 2013-02-21 |
AU2011276362B2 (en) | 2016-03-17 |
WO2012006240A1 (en) | 2012-01-12 |
US9566574B2 (en) | 2017-02-14 |
BR112013000261A2 (pt) | 2017-05-16 |
CN102971451B (zh) | 2016-09-14 |
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