WO2013021681A1 - 直接液体型燃料電池用触媒の製造方法ならびに該方法により製造された触媒およびその用途 - Google Patents
直接液体型燃料電池用触媒の製造方法ならびに該方法により製造された触媒およびその用途 Download PDFInfo
- Publication number
- WO2013021681A1 WO2013021681A1 PCT/JP2012/059375 JP2012059375W WO2013021681A1 WO 2013021681 A1 WO2013021681 A1 WO 2013021681A1 JP 2012059375 W JP2012059375 W JP 2012059375W WO 2013021681 A1 WO2013021681 A1 WO 2013021681A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- catalyst
- fuel cell
- liquid fuel
- direct liquid
- transition metal
- Prior art date
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 234
- 239000000446 fuel Substances 0.000 title claims abstract description 174
- 239000007788 liquid Substances 0.000 title claims abstract description 151
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 59
- 238000000034 method Methods 0.000 title claims abstract description 35
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 130
- 150000001875 compounds Chemical class 0.000 claims abstract description 83
- 150000003624 transition metals Chemical class 0.000 claims abstract description 66
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 47
- 239000000203 mixture Substances 0.000 claims abstract description 34
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 28
- 239000012018 catalyst precursor Substances 0.000 claims abstract description 24
- 238000002156 mixing Methods 0.000 claims abstract description 16
- 150000002894 organic compounds Chemical class 0.000 claims abstract description 7
- 230000000737 periodic effect Effects 0.000 claims abstract description 7
- 239000012528 membrane Substances 0.000 claims description 74
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 54
- -1 nitrogen-containing organic compound Chemical class 0.000 claims description 53
- 239000003792 electrolyte Substances 0.000 claims description 51
- 229910052799 carbon Inorganic materials 0.000 claims description 44
- 229910052760 oxygen Inorganic materials 0.000 claims description 38
- 239000001301 oxygen Substances 0.000 claims description 38
- 229910052751 metal Inorganic materials 0.000 claims description 35
- 239000002184 metal Substances 0.000 claims description 35
- 239000002904 solvent Substances 0.000 claims description 32
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 16
- 239000000126 substance Substances 0.000 claims description 15
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 12
- 125000004429 atom Chemical group 0.000 claims description 12
- 239000012298 atmosphere Substances 0.000 claims description 11
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims description 11
- 229910052720 vanadium Inorganic materials 0.000 claims description 11
- 239000002253 acid Substances 0.000 claims description 10
- 239000010936 titanium Substances 0.000 claims description 10
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 9
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 9
- 229910052719 titanium Inorganic materials 0.000 claims description 9
- 229910052742 iron Inorganic materials 0.000 claims description 8
- 229910001507 metal halide Inorganic materials 0.000 claims description 8
- 150000005309 metal halides Chemical class 0.000 claims description 8
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 7
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 7
- 229910052715 tantalum Inorganic materials 0.000 claims description 7
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 claims description 7
- 229910052726 zirconium Inorganic materials 0.000 claims description 7
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 6
- 229910052804 chromium Inorganic materials 0.000 claims description 6
- 239000011651 chromium Substances 0.000 claims description 6
- 125000005594 diketone group Chemical group 0.000 claims description 6
- 239000010411 electrocatalyst Substances 0.000 claims description 6
- WQYVRQLZKVEZGA-UHFFFAOYSA-N hypochlorite Chemical class Cl[O-] WQYVRQLZKVEZGA-UHFFFAOYSA-N 0.000 claims description 6
- 229910052759 nickel Inorganic materials 0.000 claims description 6
- 229910052758 niobium Inorganic materials 0.000 claims description 6
- 239000010955 niobium Substances 0.000 claims description 6
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims description 6
- 229910017052 cobalt Inorganic materials 0.000 claims description 5
- 239000010941 cobalt Substances 0.000 claims description 5
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 5
- 229910021480 group 4 element Inorganic materials 0.000 claims description 5
- 229910021478 group 5 element Inorganic materials 0.000 claims description 5
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 4
- 239000013522 chelant Substances 0.000 claims description 4
- 229910052748 manganese Inorganic materials 0.000 claims description 4
- 239000011572 manganese Substances 0.000 claims description 4
- 229910001960 metal nitrate Inorganic materials 0.000 claims description 4
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical class OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 claims description 4
- 150000001805 chlorine compounds Chemical class 0.000 claims description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims 5
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 claims 1
- 230000007423 decrease Effects 0.000 abstract description 11
- 210000004027 cell Anatomy 0.000 description 121
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 75
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 37
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 33
- 239000007789 gas Substances 0.000 description 28
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 27
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 24
- 229920000557 Nafion® Polymers 0.000 description 21
- 239000002245 particle Substances 0.000 description 19
- 239000000243 solution Substances 0.000 description 19
- 238000010438 heat treatment Methods 0.000 description 17
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 16
- 229910052697 platinum Inorganic materials 0.000 description 16
- 230000000694 effects Effects 0.000 description 14
- 238000009792 diffusion process Methods 0.000 description 13
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 description 12
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 12
- 239000004020 conductor Substances 0.000 description 12
- 238000006722 reduction reaction Methods 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 12
- 239000007864 aqueous solution Substances 0.000 description 11
- 229920000642 polymer Polymers 0.000 description 11
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 10
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 10
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 10
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 9
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 9
- 238000002360 preparation method Methods 0.000 description 9
- 239000000047 product Substances 0.000 description 9
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 8
- 229910052786 argon Inorganic materials 0.000 description 8
- 239000006229 carbon black Substances 0.000 description 8
- 239000000463 material Substances 0.000 description 8
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 description 8
- 210000000170 cell membrane Anatomy 0.000 description 7
- 239000011261 inert gas Substances 0.000 description 7
- 230000001590 oxidative effect Effects 0.000 description 7
- RPESBQCJGHJMTK-UHFFFAOYSA-I pentachlorovanadium Chemical compound [Cl-].[Cl-].[Cl-].[Cl-].[Cl-].[V+5] RPESBQCJGHJMTK-UHFFFAOYSA-I 0.000 description 7
- OJVAMHKKJGICOG-UHFFFAOYSA-N 2,5-hexanedione Chemical compound CC(=O)CCC(C)=O OJVAMHKKJGICOG-UHFFFAOYSA-N 0.000 description 6
- 239000004471 Glycine Substances 0.000 description 6
- 229910021550 Vanadium Chloride Inorganic materials 0.000 description 6
- 150000004703 alkoxides Chemical class 0.000 description 6
- 238000011156 evaluation Methods 0.000 description 6
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 6
- 229920000128 polypyrrole Polymers 0.000 description 6
- 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 5
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 5
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 5
- 230000003197 catalytic effect Effects 0.000 description 5
- 229920001940 conductive polymer Polymers 0.000 description 5
- 239000006185 dispersion Substances 0.000 description 5
- 235000019253 formic acid Nutrition 0.000 description 5
- 239000010439 graphite Substances 0.000 description 5
- 229910002804 graphite Inorganic materials 0.000 description 5
- 239000004570 mortar (masonry) Substances 0.000 description 5
- 239000007800 oxidant agent Substances 0.000 description 5
- 238000000634 powder X-ray diffraction Methods 0.000 description 5
- 238000005507 spraying Methods 0.000 description 5
- 229910001260 Pt alloy Inorganic materials 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 239000002612 dispersion medium Substances 0.000 description 4
- 238000007731 hot pressing Methods 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 4
- 239000003446 ligand Substances 0.000 description 4
- 150000004767 nitrides Chemical class 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 229920000767 polyaniline Polymers 0.000 description 4
- 229920000123 polythiophene Polymers 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 4
- 239000007921 spray Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 125000000542 sulfonic acid group Chemical group 0.000 description 4
- TYKCBTYOMAUNLH-MTOQALJVSA-J (z)-4-oxopent-2-en-2-olate;titanium(4+) Chemical compound [Ti+4].C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O TYKCBTYOMAUNLH-MTOQALJVSA-J 0.000 description 3
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 3
- 229910021554 Chromium(II) chloride Inorganic materials 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- DKKCQDROTDCQOR-UHFFFAOYSA-L Ferrous lactate Chemical compound [Fe+2].CC(O)C([O-])=O.CC(O)C([O-])=O DKKCQDROTDCQOR-UHFFFAOYSA-L 0.000 description 3
- 229910021577 Iron(II) chloride Inorganic materials 0.000 description 3
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 3
- QNAYBMKLOCPYGJ-REOHCLBHSA-N L-alanine Chemical compound C[C@H](N)C(O)=O QNAYBMKLOCPYGJ-REOHCLBHSA-N 0.000 description 3
- KDXKERNSBIXSRK-YFKPBYRVSA-N L-lysine Chemical compound NCCCC[C@H](N)C(O)=O KDXKERNSBIXSRK-YFKPBYRVSA-N 0.000 description 3
- KDXKERNSBIXSRK-UHFFFAOYSA-N Lysine Natural products NCCCCC(N)C(O)=O KDXKERNSBIXSRK-UHFFFAOYSA-N 0.000 description 3
- 239000004472 Lysine Substances 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 241000282320 Panthera leo Species 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 3
- XFJRTXJMYXFAEE-UHFFFAOYSA-K [Cr+3].CC(O)C([O-])=O.CC(O)C([O-])=O.CC(O)C([O-])=O Chemical compound [Cr+3].CC(O)C([O-])=O.CC(O)C([O-])=O.CC(O)C([O-])=O XFJRTXJMYXFAEE-UHFFFAOYSA-K 0.000 description 3
- WDNIVTZNAPEMHF-UHFFFAOYSA-N acetic acid;chromium Chemical compound [Cr].CC(O)=O.CC(O)=O WDNIVTZNAPEMHF-UHFFFAOYSA-N 0.000 description 3
- 235000004279 alanine Nutrition 0.000 description 3
- 235000001014 amino acid Nutrition 0.000 description 3
- 229940024606 amino acid Drugs 0.000 description 3
- 150000003862 amino acid derivatives Chemical class 0.000 description 3
- 150000001413 amino acids Chemical class 0.000 description 3
- BTANRVKWQNVYAZ-UHFFFAOYSA-N butan-2-ol Chemical compound CCC(C)O BTANRVKWQNVYAZ-UHFFFAOYSA-N 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- QSWDMMVNRMROPK-UHFFFAOYSA-K chromium(3+) trichloride Chemical compound [Cl-].[Cl-].[Cl-].[Cr+3] QSWDMMVNRMROPK-UHFFFAOYSA-K 0.000 description 3
- WYYQVWLEPYFFLP-UHFFFAOYSA-K chromium(3+);triacetate Chemical compound [Cr+3].CC([O-])=O.CC([O-])=O.CC([O-])=O WYYQVWLEPYFFLP-UHFFFAOYSA-K 0.000 description 3
- XBWRJSSJWDOUSJ-UHFFFAOYSA-L chromium(ii) chloride Chemical compound Cl[Cr]Cl XBWRJSSJWDOUSJ-UHFFFAOYSA-L 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 150000004696 coordination complex Chemical class 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 229910001873 dinitrogen Inorganic materials 0.000 description 3
- 229910001882 dioxygen Inorganic materials 0.000 description 3
- 238000000921 elemental analysis Methods 0.000 description 3
- 239000004225 ferrous lactate Substances 0.000 description 3
- 235000013925 ferrous lactate Nutrition 0.000 description 3
- 125000000524 functional group Chemical group 0.000 description 3
- 229910052735 hafnium Inorganic materials 0.000 description 3
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 description 3
- 229910052734 helium Inorganic materials 0.000 description 3
- 239000001307 helium Substances 0.000 description 3
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 3
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 description 3
- LNOZJRCUHSPCDZ-UHFFFAOYSA-L iron(ii) acetate Chemical compound [Fe+2].CC([O-])=O.CC([O-])=O LNOZJRCUHSPCDZ-UHFFFAOYSA-L 0.000 description 3
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 3
- 239000003273 ketjen black Substances 0.000 description 3
- 239000012046 mixed solvent Substances 0.000 description 3
- LZRGWUCHXWALGY-UHFFFAOYSA-N niobium(5+);propan-2-olate Chemical compound [Nb+5].CC(C)[O-].CC(C)[O-].CC(C)[O-].CC(C)[O-].CC(C)[O-] LZRGWUCHXWALGY-UHFFFAOYSA-N 0.000 description 3
- ZTILUDNICMILKJ-UHFFFAOYSA-N niobium(v) ethoxide Chemical compound CCO[Nb](OCC)(OCC)(OCC)OCC ZTILUDNICMILKJ-UHFFFAOYSA-N 0.000 description 3
- CMOAHYOGLLEOGO-UHFFFAOYSA-N oxozirconium;dihydrochloride Chemical compound Cl.Cl.[Zr]=O CMOAHYOGLLEOGO-UHFFFAOYSA-N 0.000 description 3
- 125000004430 oxygen atom Chemical group O* 0.000 description 3
- 239000005518 polymer electrolyte Substances 0.000 description 3
- 239000000276 potassium ferrocyanide Substances 0.000 description 3
- BZXLPZMNHQWSNR-UHFFFAOYSA-N propan-2-olate;tantalum(5+) Chemical compound [Ta+5].CC(C)[O-].CC(C)[O-].CC(C)[O-].CC(C)[O-].CC(C)[O-] BZXLPZMNHQWSNR-UHFFFAOYSA-N 0.000 description 3
- ZGSOBQAJAUGRBK-UHFFFAOYSA-N propan-2-olate;zirconium(4+) Chemical compound [Zr+4].CC(C)[O-].CC(C)[O-].CC(C)[O-].CC(C)[O-] ZGSOBQAJAUGRBK-UHFFFAOYSA-N 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- ZXQVPEBHZMCRMC-UHFFFAOYSA-R tetraazanium;iron(2+);hexacyanide Chemical compound [NH4+].[NH4+].[NH4+].[NH4+].[Fe+2].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] ZXQVPEBHZMCRMC-UHFFFAOYSA-R 0.000 description 3
- XOGGUFAVLNCTRS-UHFFFAOYSA-N tetrapotassium;iron(2+);hexacyanide Chemical compound [K+].[K+].[K+].[K+].[Fe+2].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] XOGGUFAVLNCTRS-UHFFFAOYSA-N 0.000 description 3
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 3
- YARHBRUWMYJLHY-UHFFFAOYSA-Q triazanium;iron(3+);hexacyanide Chemical compound [NH4+].[NH4+].[NH4+].[Fe+3].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] YARHBRUWMYJLHY-UHFFFAOYSA-Q 0.000 description 3
- YOBOXHGSEJBUPB-MTOQALJVSA-N (z)-4-hydroxypent-3-en-2-one;zirconium Chemical compound [Zr].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O YOBOXHGSEJBUPB-MTOQALJVSA-N 0.000 description 2
- GEYOCULIXLDCMW-UHFFFAOYSA-N 1,2-phenylenediamine Chemical compound NC1=CC=CC=C1N GEYOCULIXLDCMW-UHFFFAOYSA-N 0.000 description 2
- 125000001140 1,4-phenylene group Chemical group [H]C1=C([H])C([*:2])=C([H])C([H])=C1[*:1] 0.000 description 2
- VWBVCOPVKXNMMZ-UHFFFAOYSA-N 1,5-diaminoanthracene-9,10-dione Chemical compound O=C1C2=C(N)C=CC=C2C(=O)C2=C1C=CC=C2N VWBVCOPVKXNMMZ-UHFFFAOYSA-N 0.000 description 2
- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical compound CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 0.000 description 2
- KSNGEYQWLMRSIR-UHFFFAOYSA-L 2-hydroxypropanoate;manganese(2+) Chemical compound [Mn+2].CC(O)C([O-])=O.CC(O)C([O-])=O KSNGEYQWLMRSIR-UHFFFAOYSA-L 0.000 description 2
- KDSNLYIMUZNERS-UHFFFAOYSA-N 2-methylpropanamine Chemical compound CC(C)CN KDSNLYIMUZNERS-UHFFFAOYSA-N 0.000 description 2
- HCFAJYNVAYBARA-UHFFFAOYSA-N 4-heptanone Chemical compound CCCC(=O)CCC HCFAJYNVAYBARA-UHFFFAOYSA-N 0.000 description 2
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 2
- FIPWRIJSWJWJAI-UHFFFAOYSA-N Butyl carbitol 6-propylpiperonyl ether Chemical compound C1=C(CCC)C(COCCOCCOCCCC)=CC2=C1OCO2 FIPWRIJSWJWJAI-UHFFFAOYSA-N 0.000 description 2
- XMWRBQBLMFGWIX-UHFFFAOYSA-N C60 fullerene Chemical compound C12=C3C(C4=C56)=C7C8=C5C5=C9C%10=C6C6=C4C1=C1C4=C6C6=C%10C%10=C9C9=C%11C5=C8C5=C8C7=C3C3=C7C2=C1C1=C2C4=C6C4=C%10C6=C9C9=C%11C5=C5C8=C3C3=C7C1=C1C2=C4C6=C2C9=C5C3=C12 XMWRBQBLMFGWIX-UHFFFAOYSA-N 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 229910021556 Chromium(III) chloride Inorganic materials 0.000 description 2
- 229910021580 Cobalt(II) chloride Inorganic materials 0.000 description 2
- 229910021581 Cobalt(III) chloride Inorganic materials 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- FFEARJCKVFRZRR-BYPYZUCNSA-N L-methionine Chemical compound CSCC[C@H](N)C(O)=O FFEARJCKVFRZRR-BYPYZUCNSA-N 0.000 description 2
- OUYCCCASQSFEME-QMMMGPOBSA-N L-tyrosine Chemical compound OC(=O)[C@@H](N)CC1=CC=C(O)C=C1 OUYCCCASQSFEME-QMMMGPOBSA-N 0.000 description 2
- 229910021380 Manganese Chloride Inorganic materials 0.000 description 2
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 description 2
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical class N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 2
- XITGHTRVSNMXOD-UHFFFAOYSA-N [Nb].ClOCl Chemical compound [Nb].ClOCl XITGHTRVSNMXOD-UHFFFAOYSA-N 0.000 description 2
- PBNNHBMLMRHZQR-UHFFFAOYSA-A [V+5].[V+5].[V+5].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O.[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O.[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O.[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O.[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O Chemical compound [V+5].[V+5].[V+5].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O.[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O.[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O.[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O.[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O PBNNHBMLMRHZQR-UHFFFAOYSA-A 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 125000003545 alkoxy group Chemical group 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical compound COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 description 2
- 239000011324 bead Substances 0.000 description 2
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 description 2
- 150000001721 carbon Chemical group 0.000 description 2
- 239000002134 carbon nanofiber Substances 0.000 description 2
- 229910021393 carbon nanotube Inorganic materials 0.000 description 2
- 239000002041 carbon nanotube Substances 0.000 description 2
- 239000003575 carbonaceous material Substances 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- KSGWBGANTWHAEE-UHFFFAOYSA-N chloro hypochlorite tantalum Chemical compound [Ta].ClOCl KSGWBGANTWHAEE-UHFFFAOYSA-N 0.000 description 2
- XFVGXQSSXWIWIO-UHFFFAOYSA-N chloro hypochlorite;titanium Chemical compound [Ti].ClOCl XFVGXQSSXWIWIO-UHFFFAOYSA-N 0.000 description 2
- PHFQLYPOURZARY-UHFFFAOYSA-N chromium trinitrate Chemical compound [Cr+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O PHFQLYPOURZARY-UHFFFAOYSA-N 0.000 description 2
- 235000007831 chromium(III) chloride Nutrition 0.000 description 2
- 239000011636 chromium(III) chloride Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 description 2
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 2
- VPUKOWSPRKCWBV-UHFFFAOYSA-L cobalt(2+);2-hydroxypropanoate Chemical compound [Co+2].CC(O)C([O-])=O.CC(O)C([O-])=O VPUKOWSPRKCWBV-UHFFFAOYSA-L 0.000 description 2
- UBEWDCMIDFGDOO-UHFFFAOYSA-N cobalt(2+);cobalt(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[Co+2].[Co+3].[Co+3] UBEWDCMIDFGDOO-UHFFFAOYSA-N 0.000 description 2
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 description 2
- QSQUFRGBXGXOHF-UHFFFAOYSA-N cobalt(iii) nitrate Chemical compound [Co].O[N+]([O-])=O.O[N+]([O-])=O.O[N+]([O-])=O QSQUFRGBXGXOHF-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- PAFZNILMFXTMIY-UHFFFAOYSA-N cyclohexylamine Chemical compound NC1CCCCC1 PAFZNILMFXTMIY-UHFFFAOYSA-N 0.000 description 2
- 238000005238 degreasing Methods 0.000 description 2
- QDOXWKRWXJOMAK-UHFFFAOYSA-N dichromium trioxide Chemical compound O=[Cr]O[Cr]=O QDOXWKRWXJOMAK-UHFFFAOYSA-N 0.000 description 2
- ASBGGHMVAMBCOR-UHFFFAOYSA-N ethanolate;zirconium(4+) Chemical compound [Zr+4].CC[O-].CC[O-].CC[O-].CC[O-] ASBGGHMVAMBCOR-UHFFFAOYSA-N 0.000 description 2
- HHFAWKCIHAUFRX-UHFFFAOYSA-N ethoxide Chemical compound CC[O-] HHFAWKCIHAUFRX-UHFFFAOYSA-N 0.000 description 2
- 239000010408 film Substances 0.000 description 2
- 229910003472 fullerene Inorganic materials 0.000 description 2
- YMAWOPBAYDPSLA-UHFFFAOYSA-N glycylglycine Chemical compound [NH3+]CC(=O)NCC([O-])=O YMAWOPBAYDPSLA-UHFFFAOYSA-N 0.000 description 2
- YCJQNNVSZNFWAH-UHFFFAOYSA-J hafnium(4+);tetraiodide Chemical compound I[Hf](I)(I)I YCJQNNVSZNFWAH-UHFFFAOYSA-J 0.000 description 2
- 150000004820 halides Chemical class 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- LIKBJVNGSGBSGK-UHFFFAOYSA-N iron(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Fe+3].[Fe+3] LIKBJVNGSGBSGK-UHFFFAOYSA-N 0.000 description 2
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 2
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 2
- MLFHJEHSLIIPHL-UHFFFAOYSA-N isoamyl acetate Chemical compound CC(C)CCOC(C)=O MLFHJEHSLIIPHL-UHFFFAOYSA-N 0.000 description 2
- 238000004898 kneading Methods 0.000 description 2
- 229940071125 manganese acetate Drugs 0.000 description 2
- 235000002867 manganese chloride Nutrition 0.000 description 2
- 239000011565 manganese chloride Substances 0.000 description 2
- 229940099607 manganese chloride Drugs 0.000 description 2
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- QASMZJKUEABJNR-UHFFFAOYSA-N methanolate;tantalum(5+) Chemical compound [Ta+5].[O-]C.[O-]C.[O-]C.[O-]C.[O-]C QASMZJKUEABJNR-UHFFFAOYSA-N 0.000 description 2
- 229930182817 methionine Natural products 0.000 description 2
- 150000007522 mineralic acids Chemical class 0.000 description 2
- 239000002116 nanohorn Substances 0.000 description 2
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 235000019645 odor Nutrition 0.000 description 2
- SOWBFZRMHSNYGE-UHFFFAOYSA-N oxamic acid Chemical compound NC(=O)C(O)=O SOWBFZRMHSNYGE-UHFFFAOYSA-N 0.000 description 2
- UPWOEMHINGJHOB-UHFFFAOYSA-N oxo(oxocobaltiooxy)cobalt Chemical compound O=[Co]O[Co]=O UPWOEMHINGJHOB-UHFFFAOYSA-N 0.000 description 2
- YHBDIEWMOMLKOO-UHFFFAOYSA-I pentachloroniobium Chemical compound Cl[Nb](Cl)(Cl)(Cl)Cl YHBDIEWMOMLKOO-UHFFFAOYSA-I 0.000 description 2
- FWIYBTVHGYLSAZ-UHFFFAOYSA-I pentaiodoniobium Chemical compound I[Nb](I)(I)(I)I FWIYBTVHGYLSAZ-UHFFFAOYSA-I 0.000 description 2
- XNLICIUVMPYHGG-UHFFFAOYSA-N pentan-2-one Chemical compound CCCC(C)=O XNLICIUVMPYHGG-UHFFFAOYSA-N 0.000 description 2
- FDPIMTJIUBPUKL-UHFFFAOYSA-N pentan-3-one Chemical compound CCC(=O)CC FDPIMTJIUBPUKL-UHFFFAOYSA-N 0.000 description 2
- PGMYKACGEOXYJE-UHFFFAOYSA-N pentyl acetate Chemical compound CCCCCOC(C)=O PGMYKACGEOXYJE-UHFFFAOYSA-N 0.000 description 2
- 229960005235 piperonyl butoxide Drugs 0.000 description 2
- 229920001197 polyacetylene Polymers 0.000 description 2
- OGHBATFHNDZKSO-UHFFFAOYSA-N propan-2-olate Chemical compound CC(C)[O-] OGHBATFHNDZKSO-UHFFFAOYSA-N 0.000 description 2
- WRHZVMBBRYBTKZ-UHFFFAOYSA-N pyrrole-2-carboxylic acid Chemical compound OC(=O)C1=CC=CN1 WRHZVMBBRYBTKZ-UHFFFAOYSA-N 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- OEIMLTQPLAGXMX-UHFFFAOYSA-I tantalum(v) chloride Chemical compound Cl[Ta](Cl)(Cl)(Cl)Cl OEIMLTQPLAGXMX-UHFFFAOYSA-I 0.000 description 2
- HSXKFDGTKKAEHL-UHFFFAOYSA-N tantalum(v) ethoxide Chemical compound [Ta+5].CC[O-].CC[O-].CC[O-].CC[O-].CC[O-] HSXKFDGTKKAEHL-UHFFFAOYSA-N 0.000 description 2
- TXEYQDLBPFQVAA-UHFFFAOYSA-N tetrafluoromethane Chemical compound FC(F)(F)F TXEYQDLBPFQVAA-UHFFFAOYSA-N 0.000 description 2
- 150000003609 titanium compounds Chemical class 0.000 description 2
- JMXKSZRRTHPKDL-UHFFFAOYSA-N titanium ethoxide Chemical compound [Ti+4].CC[O-].CC[O-].CC[O-].CC[O-] JMXKSZRRTHPKDL-UHFFFAOYSA-N 0.000 description 2
- IEKWPPTXWFKANS-UHFFFAOYSA-K trichlorocobalt Chemical compound Cl[Co](Cl)Cl IEKWPPTXWFKANS-UHFFFAOYSA-K 0.000 description 2
- OUYCCCASQSFEME-UHFFFAOYSA-N tyrosine Natural products OC(=O)C(N)CC1=CC=C(O)C=C1 OUYCCCASQSFEME-UHFFFAOYSA-N 0.000 description 2
- UUUGYDOQQLOJQA-UHFFFAOYSA-L vanadyl sulfate Chemical compound [V+2]=O.[O-]S([O-])(=O)=O UUUGYDOQQLOJQA-UHFFFAOYSA-L 0.000 description 2
- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical compound Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 0.000 description 2
- MTCFGRXMJLQNBG-REOHCLBHSA-N (2S)-2-Amino-3-hydroxypropansäure Chemical compound OC[C@H](N)C(O)=O MTCFGRXMJLQNBG-REOHCLBHSA-N 0.000 description 1
- MFWFDRBPQDXFRC-LNTINUHCSA-N (z)-4-hydroxypent-3-en-2-one;vanadium Chemical compound [V].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O MFWFDRBPQDXFRC-LNTINUHCSA-N 0.000 description 1
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 description 1
- UALKQROXOHJHFG-UHFFFAOYSA-N 1-ethoxy-3-methylbenzene Chemical compound CCOC1=CC=CC(C)=C1 UALKQROXOHJHFG-UHFFFAOYSA-N 0.000 description 1
- KYWMCFOWDYFYLV-UHFFFAOYSA-N 1h-imidazole-2-carboxylic acid Chemical compound OC(=O)C1=NC=CN1 KYWMCFOWDYFYLV-UHFFFAOYSA-N 0.000 description 1
- TUFKHKZLBZWCAW-UHFFFAOYSA-N 2-(1-ethenoxypropan-2-yloxy)ethanesulfonyl fluoride Chemical compound C=COCC(C)OCCS(F)(=O)=O TUFKHKZLBZWCAW-UHFFFAOYSA-N 0.000 description 1
- PTTPXKJBFFKCEK-UHFFFAOYSA-N 2-Methyl-4-heptanone Chemical compound CC(C)CC(=O)CC(C)C PTTPXKJBFFKCEK-UHFFFAOYSA-N 0.000 description 1
- AVMSWPWPYJVYKY-UHFFFAOYSA-N 2-Methylpropyl formate Chemical compound CC(C)COC=O AVMSWPWPYJVYKY-UHFFFAOYSA-N 0.000 description 1
- QQZOPKMRPOGIEB-UHFFFAOYSA-N 2-Oxohexane Chemical compound CCCCC(C)=O QQZOPKMRPOGIEB-UHFFFAOYSA-N 0.000 description 1
- QMOQBVOBWVNSNO-UHFFFAOYSA-N 2-[[2-[[2-[(2-azaniumylacetyl)amino]acetyl]amino]acetyl]amino]acetate Chemical compound NCC(=O)NCC(=O)NCC(=O)NCC(O)=O QMOQBVOBWVNSNO-UHFFFAOYSA-N 0.000 description 1
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 1
- OAVRWNUUOUXDFH-UHFFFAOYSA-H 2-hydroxypropane-1,2,3-tricarboxylate;manganese(2+) Chemical compound [Mn+2].[Mn+2].[Mn+2].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O.[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O OAVRWNUUOUXDFH-UHFFFAOYSA-H 0.000 description 1
- IPBBPIKNVOONQZ-UHFFFAOYSA-L 2-hydroxypropanoate;nickel(2+) Chemical compound [Ni+2].CC(O)C([O-])=O.CC(O)C([O-])=O IPBBPIKNVOONQZ-UHFFFAOYSA-L 0.000 description 1
- PURTUPNWTLPILZ-UHFFFAOYSA-N 2-hydroxypropanoic acid;nickel Chemical compound [Ni].CC(O)C(O)=O.CC(O)C(O)=O PURTUPNWTLPILZ-UHFFFAOYSA-N 0.000 description 1
- SNOJPWLNAMAYSX-UHFFFAOYSA-N 2-methylpropan-1-ol;titanium Chemical compound [Ti].CC(C)CO.CC(C)CO.CC(C)CO.CC(C)CO SNOJPWLNAMAYSX-UHFFFAOYSA-N 0.000 description 1
- YMJMHACKPJBWMC-UHFFFAOYSA-N 2-methylpropan-1-olate;zirconium(4+) Chemical compound [Zr+4].CC(C)C[O-].CC(C)C[O-].CC(C)C[O-].CC(C)C[O-] YMJMHACKPJBWMC-UHFFFAOYSA-N 0.000 description 1
- GVHUQXQVSWGYSH-UHFFFAOYSA-N 4-(3-bromophenyl)-2-methyl-1,3-thiazole Chemical compound S1C(C)=NC(C=2C=C(Br)C=CC=2)=C1 GVHUQXQVSWGYSH-UHFFFAOYSA-N 0.000 description 1
- MFWFDRBPQDXFRC-UHFFFAOYSA-N 4-hydroxypent-3-en-2-one;vanadium Chemical compound [V].CC(O)=CC(C)=O.CC(O)=CC(C)=O.CC(O)=CC(C)=O MFWFDRBPQDXFRC-UHFFFAOYSA-N 0.000 description 1
- ODHCTXKNWHHXJC-VKHMYHEASA-N 5-oxo-L-proline Chemical compound OC(=O)[C@@H]1CCC(=O)N1 ODHCTXKNWHHXJC-VKHMYHEASA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- 239000004475 Arginine Substances 0.000 description 1
- DCXYFEDJOCDNAF-UHFFFAOYSA-N Asparagine Natural products OC(=O)C(N)CC(N)=O DCXYFEDJOCDNAF-UHFFFAOYSA-N 0.000 description 1
- 238000004438 BET method Methods 0.000 description 1
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 1
- FERIUCNNQQJTOY-UHFFFAOYSA-M Butyrate Chemical compound CCCC([O-])=O FERIUCNNQQJTOY-UHFFFAOYSA-M 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 229910021555 Chromium Chloride Inorganic materials 0.000 description 1
- 229910021503 Cobalt(II) hydroxide Inorganic materials 0.000 description 1
- QSJXEFYPDANLFS-UHFFFAOYSA-N Diacetyl Chemical group CC(=O)C(C)=O QSJXEFYPDANLFS-UHFFFAOYSA-N 0.000 description 1
- MBMLMWLHJBBADN-UHFFFAOYSA-N Ferrous sulfide Chemical compound [Fe]=S MBMLMWLHJBBADN-UHFFFAOYSA-N 0.000 description 1
- WHUUTDBJXJRKMK-UHFFFAOYSA-N Glutamic acid Natural products OC(=O)C(N)CCC(O)=O WHUUTDBJXJRKMK-UHFFFAOYSA-N 0.000 description 1
- 108010008488 Glycylglycine Proteins 0.000 description 1
- SNDPXSYFESPGGJ-BYPYZUCNSA-N L-2-aminopentanoic acid Chemical compound CCC[C@H](N)C(O)=O SNDPXSYFESPGGJ-BYPYZUCNSA-N 0.000 description 1
- XUJNEKJLAYXESH-REOHCLBHSA-N L-Cysteine Chemical compound SC[C@H](N)C(O)=O XUJNEKJLAYXESH-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
- DCXYFEDJOCDNAF-REOHCLBHSA-N L-asparagine Chemical compound OC(=O)[C@@H](N)CC(N)=O DCXYFEDJOCDNAF-REOHCLBHSA-N 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
- WHUUTDBJXJRKMK-VKHMYHEASA-N L-glutamic acid Chemical compound OC(=O)[C@@H](N)CCC(O)=O WHUUTDBJXJRKMK-VKHMYHEASA-N 0.000 description 1
- ZDXPYRJPNDTMRX-VKHMYHEASA-N L-glutamine Chemical compound OC(=O)[C@@H](N)CCC(N)=O ZDXPYRJPNDTMRX-VKHMYHEASA-N 0.000 description 1
- HNDVDQJCIGZPNO-YFKPBYRVSA-N L-histidine Chemical compound OC(=O)[C@@H](N)CC1=CN=CN1 HNDVDQJCIGZPNO-YFKPBYRVSA-N 0.000 description 1
- AGPKZVBTJJNPAG-WHFBIAKZSA-N L-isoleucine Chemical compound CC[C@H](C)[C@H](N)C(O)=O AGPKZVBTJJNPAG-WHFBIAKZSA-N 0.000 description 1
- ROHFNLRQFUQHCH-YFKPBYRVSA-N L-leucine Chemical compound CC(C)C[C@H](N)C(O)=O ROHFNLRQFUQHCH-YFKPBYRVSA-N 0.000 description 1
- SNDPXSYFESPGGJ-UHFFFAOYSA-N L-norVal-OH Natural products CCCC(N)C(O)=O SNDPXSYFESPGGJ-UHFFFAOYSA-N 0.000 description 1
- COLNVLDHVKWLRT-QMMMGPOBSA-N L-phenylalanine Chemical compound OC(=O)[C@@H](N)CC1=CC=CC=C1 COLNVLDHVKWLRT-QMMMGPOBSA-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
- QIVBCDIJIAJPQS-VIFPVBQESA-N L-tryptophane Chemical compound C1=CC=C2C(C[C@H](N)C(O)=O)=CNC2=C1 QIVBCDIJIAJPQS-VIFPVBQESA-N 0.000 description 1
- KZSNJWFQEVHDMF-BYPYZUCNSA-N L-valine Chemical compound CC(C)[C@H](N)C(O)=O KZSNJWFQEVHDMF-BYPYZUCNSA-N 0.000 description 1
- ROHFNLRQFUQHCH-UHFFFAOYSA-N Leucine Natural products CC(C)CC(N)C(O)=O ROHFNLRQFUQHCH-UHFFFAOYSA-N 0.000 description 1
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 1
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 description 1
- HBDWIFWQCRXRNE-UHFFFAOYSA-N O(Br)Br.[Ta] Chemical compound O(Br)Br.[Ta] HBDWIFWQCRXRNE-UHFFFAOYSA-N 0.000 description 1
- JDQLYUOLUJVFMI-UHFFFAOYSA-N O(I)I.[Hf] Chemical compound O(I)I.[Hf] JDQLYUOLUJVFMI-UHFFFAOYSA-N 0.000 description 1
- LYDXIDCDSVRIBX-UHFFFAOYSA-N O(I)I.[V] Chemical compound O(I)I.[V] LYDXIDCDSVRIBX-UHFFFAOYSA-N 0.000 description 1
- 108010038807 Oligopeptides Proteins 0.000 description 1
- 102000015636 Oligopeptides Human genes 0.000 description 1
- DIQMPQMYFZXDAX-UHFFFAOYSA-N Pentyl formate Chemical compound CCCCCOC=O DIQMPQMYFZXDAX-UHFFFAOYSA-N 0.000 description 1
- SIOXPEMLGUPBBT-UHFFFAOYSA-N Picolinic acid Natural products OC(=O)C1=CC=CC=N1 SIOXPEMLGUPBBT-UHFFFAOYSA-N 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- 229910002848 Pt–Ru Inorganic materials 0.000 description 1
- ODHCTXKNWHHXJC-GSVOUGTGSA-N Pyroglutamic acid Natural products OC(=O)[C@H]1CCC(=O)N1 ODHCTXKNWHHXJC-GSVOUGTGSA-N 0.000 description 1
- MTCFGRXMJLQNBG-UHFFFAOYSA-N Serine Natural products OCC(N)C(O)=O MTCFGRXMJLQNBG-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 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
- 239000007983 Tris buffer Substances 0.000 description 1
- QIVBCDIJIAJPQS-UHFFFAOYSA-N Tryptophan Natural products C1=CC=C2C(CC(N)C(O)=O)=CNC2=C1 QIVBCDIJIAJPQS-UHFFFAOYSA-N 0.000 description 1
- KZSNJWFQEVHDMF-UHFFFAOYSA-N Valine Natural products CC(C)C(N)C(O)=O KZSNJWFQEVHDMF-UHFFFAOYSA-N 0.000 description 1
- 229910021553 Vanadium(V) chloride Inorganic materials 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- WZOZCAZYAWIWQO-UHFFFAOYSA-N [Ni].[Ni]=O Chemical class [Ni].[Ni]=O WZOZCAZYAWIWQO-UHFFFAOYSA-N 0.000 description 1
- XHCLAFWTIXFWPH-UHFFFAOYSA-N [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] XHCLAFWTIXFWPH-UHFFFAOYSA-N 0.000 description 1
- DCWGMKCIAMRMKU-UHFFFAOYSA-H [OH-].[Cr+3].[Cr+3].[OH-].[OH-].[OH-].[OH-].[OH-] Chemical class [OH-].[Cr+3].[Cr+3].[OH-].[OH-].[OH-].[OH-].[OH-] DCWGMKCIAMRMKU-UHFFFAOYSA-H 0.000 description 1
- KSECJOPEZIAKMU-UHFFFAOYSA-N [S--].[S--].[S--].[S--].[S--].[V+5].[V+5] Chemical compound [S--].[S--].[S--].[S--].[S--].[V+5].[V+5] KSECJOPEZIAKMU-UHFFFAOYSA-N 0.000 description 1
- NIGVTWDAKGEUCU-UHFFFAOYSA-D [V+5].C(C)(=O)[O-].[V+5].C(C)(=O)[O-].C(C)(=O)[O-].C(C)(=O)[O-].C(C)(=O)[O-].C(C)(=O)[O-].C(C)(=O)[O-].C(C)(=O)[O-].C(C)(=O)[O-].C(C)(=O)[O-] Chemical class [V+5].C(C)(=O)[O-].[V+5].C(C)(=O)[O-].C(C)(=O)[O-].C(C)(=O)[O-].C(C)(=O)[O-].C(C)(=O)[O-].C(C)(=O)[O-].C(C)(=O)[O-].C(C)(=O)[O-].C(C)(=O)[O-] NIGVTWDAKGEUCU-UHFFFAOYSA-D 0.000 description 1
- CPLPNZFTIJOEIN-UHFFFAOYSA-I [V+5].CC([O-])=O.CC([O-])=O.CC([O-])=O.CC([O-])=O.CC([O-])=O Chemical compound [V+5].CC([O-])=O.CC([O-])=O.CC([O-])=O.CC([O-])=O.CC([O-])=O CPLPNZFTIJOEIN-UHFFFAOYSA-I 0.000 description 1
- MBJAOHZZTCXJSK-UHFFFAOYSA-N [V].BrOBr Chemical compound [V].BrOBr MBJAOHZZTCXJSK-UHFFFAOYSA-N 0.000 description 1
- DMPBOXWVTIVYCF-UHFFFAOYSA-N [Zr].BrOBr Chemical compound [Zr].BrOBr DMPBOXWVTIVYCF-UHFFFAOYSA-N 0.000 description 1
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 description 1
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 description 1
- CUJRVFIICFDLGR-UHFFFAOYSA-N acetylacetonate Chemical compound CC(=O)[CH-]C(C)=O CUJRVFIICFDLGR-UHFFFAOYSA-N 0.000 description 1
- 125000005595 acetylacetonate group Chemical group 0.000 description 1
- ODHCTXKNWHHXJC-UHFFFAOYSA-N acide pyroglutamique Natural products OC(=O)C1CCC(=O)N1 ODHCTXKNWHHXJC-UHFFFAOYSA-N 0.000 description 1
- 125000003172 aldehyde group Chemical group 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
- 150000001412 amines Chemical class 0.000 description 1
- 229940124277 aminobutyric acid Drugs 0.000 description 1
- 229940053200 antiepileptics fatty acid derivative Drugs 0.000 description 1
- ODKSFYDXXFIFQN-UHFFFAOYSA-N arginine Natural products OC(=O)C(N)CCCNC(N)=N ODKSFYDXXFIFQN-UHFFFAOYSA-N 0.000 description 1
- 235000009697 arginine Nutrition 0.000 description 1
- 235000009582 asparagine Nutrition 0.000 description 1
- 229960001230 asparagine Drugs 0.000 description 1
- 235000003704 aspartic acid Nutrition 0.000 description 1
- 235000019445 benzyl alcohol Nutrition 0.000 description 1
- OQFSQFPPLPISGP-UHFFFAOYSA-N beta-carboxyaspartic acid Natural products OC(=O)C(N)C(C(O)=O)C(O)=O OQFSQFPPLPISGP-UHFFFAOYSA-N 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- OSGJMCIQHXBIGS-UHFFFAOYSA-N bromo hypobromite hafnium Chemical compound [Hf].O(Br)Br OSGJMCIQHXBIGS-UHFFFAOYSA-N 0.000 description 1
- METCOICSHWVCSX-UHFFFAOYSA-N bromo hypobromite niobium Chemical compound [Nb].BrOBr METCOICSHWVCSX-UHFFFAOYSA-N 0.000 description 1
- LTBRWBUKPWVGFA-UHFFFAOYSA-N butan-1-olate;hafnium(4+) Chemical compound [Hf+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] LTBRWBUKPWVGFA-UHFFFAOYSA-N 0.000 description 1
- DINQVNXOZUORJS-UHFFFAOYSA-N butan-1-olate;niobium(5+) Chemical compound [Nb+5].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] DINQVNXOZUORJS-UHFFFAOYSA-N 0.000 description 1
- QORWLRPWMJEJKP-UHFFFAOYSA-N butan-1-olate;tantalum(5+) Chemical compound [Ta+5].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] QORWLRPWMJEJKP-UHFFFAOYSA-N 0.000 description 1
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 description 1
- BSDOQSMQCZQLDV-UHFFFAOYSA-N butan-1-olate;zirconium(4+) Chemical compound [Zr+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] BSDOQSMQCZQLDV-UHFFFAOYSA-N 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 150000001722 carbon compounds Chemical class 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 150000004770 chalcogenides Chemical class 0.000 description 1
- FLVFLHZPYDNHJE-UHFFFAOYSA-N chloro hypochlorite;hafnium Chemical compound [Hf].ClOCl FLVFLHZPYDNHJE-UHFFFAOYSA-N 0.000 description 1
- ZHXZNKNQUHUIGN-UHFFFAOYSA-N chloro hypochlorite;vanadium Chemical compound [V].ClOCl ZHXZNKNQUHUIGN-UHFFFAOYSA-N 0.000 description 1
- DBULDCSVZCUQIR-UHFFFAOYSA-N chromium(3+);trisulfide Chemical compound [S-2].[S-2].[S-2].[Cr+3].[Cr+3] DBULDCSVZCUQIR-UHFFFAOYSA-N 0.000 description 1
- IAQWMWUKBQPOIY-UHFFFAOYSA-N chromium(4+);oxygen(2-) Chemical compound [O-2].[O-2].[Cr+4] IAQWMWUKBQPOIY-UHFFFAOYSA-N 0.000 description 1
- 229910000424 chromium(II) oxide Inorganic materials 0.000 description 1
- 229910000151 chromium(III) phosphate Inorganic materials 0.000 description 1
- GRWVQDDAKZFPFI-UHFFFAOYSA-H chromium(III) sulfate Chemical compound [Cr+3].[Cr+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O GRWVQDDAKZFPFI-UHFFFAOYSA-H 0.000 description 1
- 229910000356 chromium(III) sulfate Inorganic materials 0.000 description 1
- 235000015217 chromium(III) sulphate Nutrition 0.000 description 1
- 239000011696 chromium(III) sulphate Substances 0.000 description 1
- AYTAKQFHWFYBMA-UHFFFAOYSA-N chromium(IV) oxide Inorganic materials O=[Cr]=O AYTAKQFHWFYBMA-UHFFFAOYSA-N 0.000 description 1
- XVHFYNOGAFYRJV-UHFFFAOYSA-L chromium(ii) oxalate Chemical compound [Cr+2].[O-]C(=O)C([O-])=O XVHFYNOGAFYRJV-UHFFFAOYSA-L 0.000 description 1
- IKZBVTPSNGOVRJ-UHFFFAOYSA-K chromium(iii) phosphate Chemical compound [Cr+3].[O-]P([O-])([O-])=O IKZBVTPSNGOVRJ-UHFFFAOYSA-K 0.000 description 1
- 150000001869 cobalt compounds Chemical class 0.000 description 1
- 229910000152 cobalt phosphate Inorganic materials 0.000 description 1
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 description 1
- ZBDSFTZNNQNSQM-UHFFFAOYSA-H cobalt(2+);diphosphate Chemical compound [Co+2].[Co+2].[Co+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O ZBDSFTZNNQNSQM-UHFFFAOYSA-H 0.000 description 1
- MULYSYXKGICWJF-UHFFFAOYSA-L cobalt(2+);oxalate Chemical compound [Co+2].[O-]C(=O)C([O-])=O MULYSYXKGICWJF-UHFFFAOYSA-L 0.000 description 1
- IUYLTEAJCNAMJK-UHFFFAOYSA-N cobalt(2+);oxygen(2-) Chemical compound [O-2].[Co+2] IUYLTEAJCNAMJK-UHFFFAOYSA-N 0.000 description 1
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(II) oxide Inorganic materials [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 1
- 229910000335 cobalt(II) sulfate Inorganic materials 0.000 description 1
- PKSIZOUDEUREFF-UHFFFAOYSA-N cobalt;dihydrate Chemical compound O.O.[Co] PKSIZOUDEUREFF-UHFFFAOYSA-N 0.000 description 1
- ILZSSCVGGYJLOG-UHFFFAOYSA-N cobaltocene Chemical compound [Co+2].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 ILZSSCVGGYJLOG-UHFFFAOYSA-N 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000008602 contraction Effects 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- XUJNEKJLAYXESH-UHFFFAOYSA-N cysteine Natural products SCC(N)C(O)=O XUJNEKJLAYXESH-UHFFFAOYSA-N 0.000 description 1
- 235000018417 cysteine Nutrition 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 1
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 1
- BADXJIPKFRBFOT-UHFFFAOYSA-N dimedone Chemical compound CC1(C)CC(=O)CC(=O)C1 BADXJIPKFRBFOT-UHFFFAOYSA-N 0.000 description 1
- HTXDPTMKBJXEOW-UHFFFAOYSA-N dioxoiridium Chemical compound O=[Ir]=O HTXDPTMKBJXEOW-UHFFFAOYSA-N 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- POLCUAVZOMRGSN-UHFFFAOYSA-N dipropyl ether Chemical compound CCCOCCC POLCUAVZOMRGSN-UHFFFAOYSA-N 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- BFIMXCBKRLYJQO-UHFFFAOYSA-N ethanolate;hafnium(4+) Chemical compound [Hf+4].CC[O-].CC[O-].CC[O-].CC[O-] BFIMXCBKRLYJQO-UHFFFAOYSA-N 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- VEPSWGHMGZQCIN-UHFFFAOYSA-H ferric oxalate Chemical compound [Fe+3].[Fe+3].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O VEPSWGHMGZQCIN-UHFFFAOYSA-H 0.000 description 1
- KTWOOEGAPBSYNW-UHFFFAOYSA-N ferrocene Chemical compound [Fe+2].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 KTWOOEGAPBSYNW-UHFFFAOYSA-N 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- BTCSSZJGUNDROE-UHFFFAOYSA-N gamma-aminobutyric acid Chemical compound NCCCC(O)=O BTCSSZJGUNDROE-UHFFFAOYSA-N 0.000 description 1
- 235000013922 glutamic acid Nutrition 0.000 description 1
- 239000004220 glutamic acid Substances 0.000 description 1
- ZDXPYRJPNDTMRX-UHFFFAOYSA-N glutamine Natural products OC(=O)C(N)CCC(N)=O ZDXPYRJPNDTMRX-UHFFFAOYSA-N 0.000 description 1
- 235000004554 glutamine Nutrition 0.000 description 1
- 108010067216 glycyl-glycyl-glycine Proteins 0.000 description 1
- XKUKSGPZAADMRA-UHFFFAOYSA-N glycyl-glycyl-glycine Natural products NCC(=O)NCC(=O)NCC(O)=O XKUKSGPZAADMRA-UHFFFAOYSA-N 0.000 description 1
- 108010001064 glycyl-glycyl-glycyl-glycine Proteins 0.000 description 1
- 229940043257 glycylglycine Drugs 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 150000002363 hafnium compounds Chemical class 0.000 description 1
- PDPJQWYGJJBYLF-UHFFFAOYSA-J hafnium tetrachloride Chemical compound Cl[Hf](Cl)(Cl)Cl PDPJQWYGJJBYLF-UHFFFAOYSA-J 0.000 description 1
- IDTQPBPCYLOMIS-UHFFFAOYSA-N hafnium(4+) 2-methylpropan-1-olate Chemical compound [Hf+4].CC(C)C[O-].CC(C)C[O-].CC(C)C[O-].CC(C)C[O-] IDTQPBPCYLOMIS-UHFFFAOYSA-N 0.000 description 1
- KIXLEMHCRGHACT-UHFFFAOYSA-N hafnium(4+);methanolate Chemical compound [Hf+4].[O-]C.[O-]C.[O-]C.[O-]C KIXLEMHCRGHACT-UHFFFAOYSA-N 0.000 description 1
- SEKCULWEIYBRLO-UHFFFAOYSA-N hafnium(4+);propan-1-olate Chemical compound [Hf+4].CCC[O-].CCC[O-].CCC[O-].CCC[O-] SEKCULWEIYBRLO-UHFFFAOYSA-N 0.000 description 1
- HRDRRWUDXWRQTB-UHFFFAOYSA-N hafnium(4+);propan-2-olate Chemical compound [Hf+4].CC(C)[O-].CC(C)[O-].CC(C)[O-].CC(C)[O-] HRDRRWUDXWRQTB-UHFFFAOYSA-N 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- CATSNJVOTSVZJV-UHFFFAOYSA-N heptan-2-one Chemical compound CCCCCC(C)=O CATSNJVOTSVZJV-UHFFFAOYSA-N 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-M hexanoate Chemical compound CCCCCC([O-])=O FUZZWVXGSFPDMH-UHFFFAOYSA-M 0.000 description 1
- HNDVDQJCIGZPNO-UHFFFAOYSA-N histidine Natural products OC(=O)C(N)CC1=CN=CN1 HNDVDQJCIGZPNO-UHFFFAOYSA-N 0.000 description 1
- 230000001939 inductive effect Effects 0.000 description 1
- 238000001095 inductively coupled plasma mass spectrometry Methods 0.000 description 1
- 229910052809 inorganic oxide Inorganic materials 0.000 description 1
- ZSENRPJNMNDGHS-UHFFFAOYSA-N iodo hypoiodite tantalum Chemical compound O(I)I.[Ta] ZSENRPJNMNDGHS-UHFFFAOYSA-N 0.000 description 1
- JMCVTQFKRIYPDK-UHFFFAOYSA-N iodo hypoiodite titanium Chemical compound O(I)I.[Ti] JMCVTQFKRIYPDK-UHFFFAOYSA-N 0.000 description 1
- VAPBTOIXFSABND-UHFFFAOYSA-N iodo hypoiodite zirconium Chemical compound [Zr].IOI VAPBTOIXFSABND-UHFFFAOYSA-N 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- 229910000457 iridium oxide Inorganic materials 0.000 description 1
- 150000002506 iron compounds Chemical class 0.000 description 1
- MVFCKEFYUDZOCX-UHFFFAOYSA-N iron(2+);dinitrate Chemical compound [Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MVFCKEFYUDZOCX-UHFFFAOYSA-N 0.000 description 1
- OWZIYWAUNZMLRT-UHFFFAOYSA-L iron(2+);oxalate Chemical compound [Fe+2].[O-]C(=O)C([O-])=O OWZIYWAUNZMLRT-UHFFFAOYSA-L 0.000 description 1
- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical compound [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 description 1
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 description 1
- KAEAMHPPLLJBKF-UHFFFAOYSA-N iron(3+) sulfide Chemical compound [S-2].[S-2].[S-2].[Fe+3].[Fe+3] KAEAMHPPLLJBKF-UHFFFAOYSA-N 0.000 description 1
- PVFSDGKDKFSOTB-UHFFFAOYSA-K iron(3+);triacetate Chemical compound [Fe+3].CC([O-])=O.CC([O-])=O.CC([O-])=O PVFSDGKDKFSOTB-UHFFFAOYSA-K 0.000 description 1
- 229910021506 iron(II) hydroxide Inorganic materials 0.000 description 1
- 229910000155 iron(II) phosphate Inorganic materials 0.000 description 1
- NPFOYSMITVOQOS-UHFFFAOYSA-K iron(III) citrate Chemical compound [Fe+3].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NPFOYSMITVOQOS-UHFFFAOYSA-K 0.000 description 1
- 229910000399 iron(III) phosphate Inorganic materials 0.000 description 1
- 229910000360 iron(III) sulfate Inorganic materials 0.000 description 1
- NCNCGGDMXMBVIA-UHFFFAOYSA-L iron(ii) hydroxide Chemical compound [OH-].[OH-].[Fe+2] NCNCGGDMXMBVIA-UHFFFAOYSA-L 0.000 description 1
- SDEKDNPYZOERBP-UHFFFAOYSA-H iron(ii) phosphate Chemical compound [Fe+2].[Fe+2].[Fe+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O SDEKDNPYZOERBP-UHFFFAOYSA-H 0.000 description 1
- GJRQTCIYDGXPES-UHFFFAOYSA-N iso-butyl acetate Natural products CC(C)COC(C)=O GJRQTCIYDGXPES-UHFFFAOYSA-N 0.000 description 1
- 229940035429 isobutyl alcohol Drugs 0.000 description 1
- FGKJLKRYENPLQH-UHFFFAOYSA-M isocaproate Chemical compound CC(C)CCC([O-])=O FGKJLKRYENPLQH-UHFFFAOYSA-M 0.000 description 1
- 229960000310 isoleucine Drugs 0.000 description 1
- AGPKZVBTJJNPAG-UHFFFAOYSA-N isoleucine Natural products CCC(C)C(N)C(O)=O AGPKZVBTJJNPAG-UHFFFAOYSA-N 0.000 description 1
- JJWLVOIRVHMVIS-UHFFFAOYSA-N isopropylamine Chemical compound CC(C)N JJWLVOIRVHMVIS-UHFFFAOYSA-N 0.000 description 1
- OQAGVSWESNCJJT-UHFFFAOYSA-N isovaleric acid methyl ester Natural products COC(=O)CC(C)C OQAGVSWESNCJJT-UHFFFAOYSA-N 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- HXEACLLIILLPRG-RXMQYKEDSA-N l-pipecolic acid Natural products OC(=O)[C@H]1CCCCN1 HXEACLLIILLPRG-RXMQYKEDSA-N 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- MJIVRKPEXXHNJT-UHFFFAOYSA-N lutidinic acid Chemical compound OC(=O)C1=CC=NC(C(O)=O)=C1 MJIVRKPEXXHNJT-UHFFFAOYSA-N 0.000 description 1
- 235000014872 manganese citrate Nutrition 0.000 description 1
- 239000011564 manganese citrate Substances 0.000 description 1
- 229940097206 manganese citrate Drugs 0.000 description 1
- 150000002697 manganese compounds Chemical class 0.000 description 1
- IPJKJLXEVHOKSE-UHFFFAOYSA-L manganese dihydroxide Chemical compound [OH-].[OH-].[Mn+2] IPJKJLXEVHOKSE-UHFFFAOYSA-L 0.000 description 1
- 229940099596 manganese sulfate Drugs 0.000 description 1
- 235000007079 manganese sulphate Nutrition 0.000 description 1
- 239000011702 manganese sulphate Substances 0.000 description 1
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- RGVLTEMOWXGQOS-UHFFFAOYSA-L manganese(2+);oxalate Chemical compound [Mn+2].[O-]C(=O)C([O-])=O RGVLTEMOWXGQOS-UHFFFAOYSA-L 0.000 description 1
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000002609 medium Substances 0.000 description 1
- 229910001509 metal bromide Inorganic materials 0.000 description 1
- 229910001510 metal chloride Inorganic materials 0.000 description 1
- 229910001511 metal iodide Inorganic materials 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 229910001463 metal phosphate Inorganic materials 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- IJCCNPITMWRYRC-UHFFFAOYSA-N methanolate;niobium(5+) Chemical compound [Nb+5].[O-]C.[O-]C.[O-]C.[O-]C.[O-]C IJCCNPITMWRYRC-UHFFFAOYSA-N 0.000 description 1
- ITNVWQNWHXEMNS-UHFFFAOYSA-N methanolate;titanium(4+) Chemical compound [Ti+4].[O-]C.[O-]C.[O-]C.[O-]C ITNVWQNWHXEMNS-UHFFFAOYSA-N 0.000 description 1
- IKGXNCHYONXJSM-UHFFFAOYSA-N methanolate;zirconium(4+) Chemical compound [Zr+4].[O-]C.[O-]C.[O-]C.[O-]C IKGXNCHYONXJSM-UHFFFAOYSA-N 0.000 description 1
- NBTOZLQBSIZIKS-UHFFFAOYSA-N methoxide Chemical compound [O-]C NBTOZLQBSIZIKS-UHFFFAOYSA-N 0.000 description 1
- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Substances CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 description 1
- CETWDUZRCINIHU-UHFFFAOYSA-N methyl-n-amyl-carbinol Natural products CCCCCC(C)O CETWDUZRCINIHU-UHFFFAOYSA-N 0.000 description 1
- YKYONYBAUNKHLG-UHFFFAOYSA-N n-Propyl acetate Natural products CCCOC(C)=O YKYONYBAUNKHLG-UHFFFAOYSA-N 0.000 description 1
- 229940078494 nickel acetate Drugs 0.000 description 1
- 229910000159 nickel phosphate Inorganic materials 0.000 description 1
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 1
- DOLZKNFSRCEOFV-UHFFFAOYSA-L nickel(2+);oxalate Chemical compound [Ni+2].[O-]C(=O)C([O-])=O DOLZKNFSRCEOFV-UHFFFAOYSA-L 0.000 description 1
- JOCJYBPHESYFOK-UHFFFAOYSA-K nickel(3+);phosphate Chemical compound [Ni+3].[O-]P([O-])([O-])=O JOCJYBPHESYFOK-UHFFFAOYSA-K 0.000 description 1
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 1
- AIYYMMQIMJOTBM-UHFFFAOYSA-L nickel(ii) acetate Chemical compound [Ni+2].CC([O-])=O.CC([O-])=O AIYYMMQIMJOTBM-UHFFFAOYSA-L 0.000 description 1
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 1
- AIBQNUOBCRIENU-UHFFFAOYSA-N nickel;dihydrate Chemical compound O.O.[Ni] AIBQNUOBCRIENU-UHFFFAOYSA-N 0.000 description 1
- 150000002822 niobium compounds Chemical class 0.000 description 1
- DSYRJFDOOSKABR-UHFFFAOYSA-I niobium(v) bromide Chemical compound [Br-].[Br-].[Br-].[Br-].[Br-].[Nb+5] DSYRJFDOOSKABR-UHFFFAOYSA-I 0.000 description 1
- MGFYIUFZLHCRTH-UHFFFAOYSA-N nitrilotriacetic acid Chemical compound OC(=O)CN(CC(O)=O)CC(O)=O MGFYIUFZLHCRTH-UHFFFAOYSA-N 0.000 description 1
- 229940110728 nitrogen / oxygen Drugs 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 description 1
- 229910052755 nonmetal Inorganic materials 0.000 description 1
- 150000002843 nonmetals Chemical class 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- OGUCKKLSDGRKSH-UHFFFAOYSA-N oxalic acid oxovanadium Chemical compound [V].[O].C(C(=O)O)(=O)O OGUCKKLSDGRKSH-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- XVOFZWCCFLVFRR-UHFFFAOYSA-N oxochromium Chemical compound [Cr]=O XVOFZWCCFLVFRR-UHFFFAOYSA-N 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 239000011236 particulate material Substances 0.000 description 1
- DFZRZMMGXSTRGC-UHFFFAOYSA-I pentaiodovanadium Chemical compound [V+5].[I-].[I-].[I-].[I-].[I-] DFZRZMMGXSTRGC-UHFFFAOYSA-I 0.000 description 1
- VLTRZXGMWDSKGL-UHFFFAOYSA-M perchlorate Inorganic materials [O-]Cl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-M 0.000 description 1
- COLNVLDHVKWLRT-UHFFFAOYSA-N phenylalanine Natural products OC(=O)C(N)CC1=CC=CC=C1 COLNVLDHVKWLRT-UHFFFAOYSA-N 0.000 description 1
- HXEACLLIILLPRG-UHFFFAOYSA-N pipecolic acid Chemical compound OC(=O)C1CCCCN1 HXEACLLIILLPRG-UHFFFAOYSA-N 0.000 description 1
- JSSXHAMIXJGYCS-UHFFFAOYSA-N piperazin-4-ium-2-carboxylate Chemical compound OC(=O)C1CNCCN1 JSSXHAMIXJGYCS-UHFFFAOYSA-N 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- IKNCGYCHMGNBCP-UHFFFAOYSA-N propan-1-olate Chemical compound CCC[O-] IKNCGYCHMGNBCP-UHFFFAOYSA-N 0.000 description 1
- HKJYVRJHDIPMQB-UHFFFAOYSA-N propan-1-olate;titanium(4+) Chemical compound CCCO[Ti](OCCC)(OCCC)OCCC HKJYVRJHDIPMQB-UHFFFAOYSA-N 0.000 description 1
- XPGAWFIWCWKDDL-UHFFFAOYSA-N propan-1-olate;zirconium(4+) Chemical compound [Zr+4].CCC[O-].CCC[O-].CCC[O-].CCC[O-] XPGAWFIWCWKDDL-UHFFFAOYSA-N 0.000 description 1
- 229940090181 propyl acetate Drugs 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- NIPZZXUFJPQHNH-UHFFFAOYSA-N pyrazine-2-carboxylic acid Chemical compound OC(=O)C1=CN=CC=N1 NIPZZXUFJPQHNH-UHFFFAOYSA-N 0.000 description 1
- ZFCHNZDUMIOWFV-UHFFFAOYSA-N pyrimidine-2-carboxylic acid Chemical compound OC(=O)C1=NC=CC=N1 ZFCHNZDUMIOWFV-UHFFFAOYSA-N 0.000 description 1
- YPOXGDJGKBXRFP-UHFFFAOYSA-N pyrimidine-4-carboxylic acid Chemical compound OC(=O)C1=CC=NC=N1 YPOXGDJGKBXRFP-UHFFFAOYSA-N 0.000 description 1
- DOYOPBSXEIZLRE-UHFFFAOYSA-N pyrrole-3-carboxylic acid Natural products OC(=O)C=1C=CNC=1 DOYOPBSXEIZLRE-UHFFFAOYSA-N 0.000 description 1
- LOAUVZALPPNFOQ-UHFFFAOYSA-N quinaldic acid Chemical compound C1=CC=CC2=NC(C(=O)O)=CC=C21 LOAUVZALPPNFOQ-UHFFFAOYSA-N 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- VSZWPYCFIRKVQL-UHFFFAOYSA-N selanylidenegallium;selenium Chemical compound [Se].[Se]=[Ga].[Se]=[Ga] VSZWPYCFIRKVQL-UHFFFAOYSA-N 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- VRRFSFYSLSPWQY-UHFFFAOYSA-N sulfanylidenecobalt Chemical compound [Co]=S VRRFSFYSLSPWQY-UHFFFAOYSA-N 0.000 description 1
- CADICXFYUNYKGD-UHFFFAOYSA-N sulfanylidenemanganese Chemical compound [Mn]=S CADICXFYUNYKGD-UHFFFAOYSA-N 0.000 description 1
- WWNBZGLDODTKEM-UHFFFAOYSA-N sulfanylidenenickel Chemical compound [Ni]=S WWNBZGLDODTKEM-UHFFFAOYSA-N 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 150000003482 tantalum compounds Chemical class 0.000 description 1
- MISXNQITXACHNJ-UHFFFAOYSA-I tantalum(5+);pentaiodide Chemical compound [I-].[I-].[I-].[I-].[I-].[Ta+5] MISXNQITXACHNJ-UHFFFAOYSA-I 0.000 description 1
- GCPVYIPZZUPXPB-UHFFFAOYSA-I tantalum(v) bromide Chemical compound Br[Ta](Br)(Br)(Br)Br GCPVYIPZZUPXPB-UHFFFAOYSA-I 0.000 description 1
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- VXKWYPOMXBVZSJ-UHFFFAOYSA-N tetramethyltin Chemical compound C[Sn](C)(C)C VXKWYPOMXBVZSJ-UHFFFAOYSA-N 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- UBZYKBZMAMTNKW-UHFFFAOYSA-J titanium tetrabromide Chemical compound Br[Ti](Br)(Br)Br UBZYKBZMAMTNKW-UHFFFAOYSA-J 0.000 description 1
- NLLZTRMHNHVXJJ-UHFFFAOYSA-J titanium tetraiodide Chemical compound I[Ti](I)(I)I NLLZTRMHNHVXJJ-UHFFFAOYSA-J 0.000 description 1
- MTAYDNKNMILFOK-UHFFFAOYSA-K titanium(3+);tribromide Chemical compound Br[Ti](Br)Br MTAYDNKNMILFOK-UHFFFAOYSA-K 0.000 description 1
- YONPGGFAJWQGJC-UHFFFAOYSA-K titanium(iii) chloride Chemical compound Cl[Ti](Cl)Cl YONPGGFAJWQGJC-UHFFFAOYSA-K 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 238000001926 trapping method Methods 0.000 description 1
- HUYLAMJIPCOVOM-UHFFFAOYSA-K triiodotitanium Chemical compound [Ti+3].[I-].[I-].[I-] HUYLAMJIPCOVOM-UHFFFAOYSA-K 0.000 description 1
- 229910001930 tungsten oxide Inorganic materials 0.000 description 1
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 description 1
- 239000004474 valine Substances 0.000 description 1
- 150000003682 vanadium compounds Chemical class 0.000 description 1
- 229910001935 vanadium oxide Inorganic materials 0.000 description 1
- 239000013585 weight reducing agent Substances 0.000 description 1
- 150000003755 zirconium compounds Chemical class 0.000 description 1
- LSWWNKUULMMMIL-UHFFFAOYSA-J zirconium(iv) bromide Chemical compound Br[Zr](Br)(Br)Br LSWWNKUULMMMIL-UHFFFAOYSA-J 0.000 description 1
- XLMQAUWIRARSJG-UHFFFAOYSA-J zirconium(iv) iodide Chemical compound [Zr+4].[I-].[I-].[I-].[I-] XLMQAUWIRARSJG-UHFFFAOYSA-J 0.000 description 1
Images
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/88—Processes of manufacture
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/745—Iron
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
- H01M4/9041—Metals or alloys
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1009—Fuel cells with solid electrolytes with one of the reactants being liquid, solid or liquid-charged
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/33—Electric or magnetic properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
- B01J37/086—Decomposition of an organometallic compound, a metal complex or a metal salt of a carboxylic acid
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Definitions
- Direct liquid fuel cells that use liquid fuels such as methanol, ethanol, formic acid, 2-propanol, and dimethyl ether as direct fuel are simple in structure and easy to handle. Application to distributed power sources is expected.
- the direct liquid fuel cell has a structure in which, for example, a proton conductive polymer electrolyte membrane is sandwiched between an anode (fuel electrode) and a cathode (air electrode).
- anode fuel electrode
- cathode air electrode
- the direct liquid fuel cell has a problem that due to the crossover of the liquid fuel, the potential at the cathode decreases with a decrease in the fuel utilization rate, and the energy conversion efficiency of the cell significantly decreases.
- the liquid fuel crossover is a phenomenon in which the liquid fuel moves from the anode to the cathode through the polymer electrolyte membrane. Since the liquid fuel that has reached the cathode is directly oxidized on the surface of the cathode catalyst, the potential at the cathode is lowered.
- Patent Document 7 discloses a carbonitride oxide obtained by mixing carbide, oxide, and nitride and heating at 500 to 1500 ° C. in a vacuum, inert or non-oxidizing atmosphere.
- the oxycarbonitride disclosed in Patent Document 7 is a thin film magnetic head ceramic substrate material, and the use of this oxycarbonitride as a catalyst has not been studied.
- platinum is useful not only as a catalyst for the fuel cell, but also as an exhaust gas treatment catalyst or an organic synthesis catalyst, platinum is expensive and has limited resources. There has been a demand for the development of a catalyst that can be substituted for use.
- the present invention relates to the following (1) to (22), for example.
- Step A in which at least a transition metal-containing compound and a nitrogen-containing organic compound are mixed to obtain a catalyst precursor composition, Including heat-treating the catalyst precursor composition at a temperature of 500 to 1100 ° C. to obtain an electrode catalyst,
- a part or all of the transition metal-containing compound is a compound containing at least one transition metal element M1 selected from Group 4 and Group 5 elements of the periodic table as a transition metal element.
- step A mixing is performed in a solvent.
- a part of the transition metal-containing compound is a compound containing at least one transition metal element M2 selected from iron, nickel, chromium, cobalt, vanadium and manganese as a transition metal element (1) to (7)
- the manufacturing method of the electrode catalyst for direct liquid fuel cells as described in any one of (7).
- the transition metal-containing compound is at least one selected from the group consisting of metal nitrates, metal acid chlorides, metal-containing organic compounds, metal halides, metal perchlorates and metal hypochlorites.
- the step C is a step of heat-treating the catalyst precursor composition at a temperature of 500 to 1100 ° C. and crushing the obtained heat-treated product to obtain an electrode catalyst (1) to (13) ).
- the method for producing an electrode catalyst for a direct liquid fuel cell according to any one of the above.
- a direct liquid fuel cell electrode having a direct liquid fuel cell catalyst layer and a porous support layer, wherein the fuel cell catalyst layer is for the direct liquid fuel cell according to (17) or (18).
- An electrode for a direct liquid fuel cell which is a catalyst layer.
- a direct liquid fuel cell membrane electrode assembly having a cathode, an anode, and an electrolyte membrane disposed between the cathode and the anode, wherein the cathode and / or the anode is a direct liquid according to (19)
- the catalyst precursor composition contains a reaction product of a transition metal-containing compound and a nitrogen-containing organic compound.
- the solubility of the reaction product in the solvent varies depending on the combination of the transition metal-containing compound, the nitrogen-containing organic compound, the solvent, and the like.
- the transition metal-containing compound, the nitrogen-containing organic compound, and the solvent may be placed in a pressurizable container such as an autoclave, and mixing may be performed while applying a pressure higher than normal pressure.
- a pressurizable container such as an autoclave
- the transition metal element M1 include titanium, zirconium, hafnium, vanadium, niobium, and tantalum. These may be used alone or in combination of two or more.
- the transition metal-containing compound preferably has at least one selected from an oxygen atom and a halogen atom.
- the transition metal-containing compound include metal phosphates, metal sulfates, metal nitrates, metal acid halides (intermediate hydrolysates of metal halides), metal halides, metal halides, and metal hypohalites.
- Metal-containing organic compounds and metal complexes, and metal nitrates, metal acid chlorides, metal-containing organic compounds, metal halides, metal perchlorates and metal hypochlorites are preferred. These may be used alone or in combination of two or more.
- the metal-containing organic compound include metal organic acid salts and metal alkoxides.
- metal halide chloride, bromide and iodide of the transition metal are preferable, and as the metal acid halide, acid chloride, acid bromide and acid iodide of the transition metal are preferable.
- the resulting catalyst becomes fine particles with a uniform particle size, and its activity is high, Titanium tetraethoxide, titanium tetrachloride, titanium oxychloride, titanium tetraisopropoxide, titanium tetraacetylacetonate, Niobium pentaethoxide, niobium pentachloride, niobium oxychloride, niobium pentaisopropoxide, Zirconium tetraethoxide, zirconium tetrachloride, zirconium oxychloride, zirconium tetraisopropoxide, zirconium tetraacetylacetonate, Tantalum pentamethoxide, tantalum pentaethoxide, tantalum pentachloride, tantalum oxychloride, tantalum pentaisopropoxide, and tantalum tetraethoxyacetylacetonate,
- transition metal-containing compound together with a transition metal-containing compound containing a transition metal element M1 of Group 4 or Group 5 of the periodic table as a transition metal element (hereinafter also referred to as “first transition metal-containing compound”),
- first transition metal-containing compound a transition metal-containing compound containing a transition metal element M1 of Group 4 or Group 5 of the periodic table as a transition metal element
- second metal a transition metal-containing compound which is an element different from the transition metal element M1 and includes at least one transition metal element M2 selected from iron, nickel, chromium, cobalt, vanadium and manganese. May also be used in combination. Use of the second transition metal-containing compound improves the performance of the resulting catalyst.
- the nitrogen-containing organic compound is not particularly limited, but a compound that can be a ligand that can coordinate to a transition metal atom in the transition metal-containing compound (preferably a compound that can form a mononuclear complex).
- a compound that can be a polydentate ligand (preferably a bidentate ligand or a tridentate ligand) (can form a chelate) is more preferable.
- the said nitrogen containing organic compound may be used individually by 1 type, and may use 2 or more types together.
- the nitrogen-containing organic compound used in the present invention preferably contains a carbonyl group.
- the carbonyl group may be contained in the nitrogen-containing organic compound as part of a functional group.
- the carbonyl group is preferably contained in the nitrogen-containing organic compound as part of a carboxyl group or an aldehyde group, and is preferably contained in the nitrogen-containing organic compound as a carboxyl group. Note that at least one carbonyl group may be included in the molecule of the nitrogen-containing organic compound, and a plurality of carbonyl groups may be included.
- the nitrogen-containing organic compound is preferable from the viewpoint of the activity of the electrode catalyst obtained by binding a nitrogen atom to the ⁇ carbon of the carbonyl group.
- Examples of the nitrogen-containing organic compound include amino acids and amino acid derivatives.
- amino acids examples include alanine, arginine, asparagine, aspartic acid, cysteine, glutamine, glutamic acid, glycine, histidine, isoleucine, leucine, lysine, methionine, phenylalanine, serine, threonine, tryptophan, tyrosine, valine, norvaline, and aminobutyric acid. Is preferred.
- pyrrole-2-carboxylic acid imidazole-2-carboxylic acid, pyrazinecarboxylic acid, piperidine-2-carboxylic acid, piperazine-2-carboxylic acid, pyrimidine-2-carboxylic acid, pyrimidine- 4-carboxylic acid, 2-pyridinecarboxylic acid, 2,4-pyridinedicarboxylic acid, 2-quinolinecarboxylic acid, and oxamic acid are preferred.
- the ratio (B / A) of the total number of carbon atoms B in the nitrogen-containing organic compound used in step A to the total number A of transition metal elements in the transition metal-containing compound used in step A is It is possible to reduce components desorbed as carbon compounds such as carbon dioxide and carbon monoxide during the heat treatment, that is, since it is possible to reduce the amount of exhaust gas during catalyst production, it is preferably 200 or less, more preferably 150 or less, more preferably 80 or less, particularly preferably 30 or less. From the viewpoint of obtaining a catalyst having a good activity, it is preferably 1 or more, more preferably 2 or more, further preferably 3 or more, particularly preferably 5 or more. It is.
- the first transition metal-containing compound and the second transition metal organic compound are used as the transition metal-containing compound
- the first transition metal-containing compound used in Step A and the second transition metal-containing compound are used.
- M1: M2 (1-a): a in terms of a molar ratio (M1: M2) between the atoms of the transition metal element M1 and the atoms of the transition metal element M2
- the range of a is usually 0 ⁇ a ⁇ 0.5, preferably 0.01 ⁇ a ⁇ 0.5, more preferably 0.02 ⁇ a ⁇ 0.4, and particularly preferably 0.05 ⁇ a ⁇ 0.5. 0.3.
- solvent examples include water, alcohols and acids.
- alcohols examples include ethanol, methanol, butanol, propanol and ethoxyethanol are preferable, and ethanol and methanol are more preferable.
- acids acetic acid, nitric acid (aqueous solution), hydrochloric acid, phosphoric acid aqueous solution and citric acid aqueous solution are preferable, and acetic acid and nitric acid are more preferable. These may be used alone or in combination of two or more.
- step A it is preferable to further mix a compound having a diketone structure. It is preferable to use a compound having a diketone structure because the transition metal-containing compound is converted into a metal complex and easily forms a uniform mixture with the nitrogen-containing compound.
- the removal of the solvent may be performed under atmospheric pressure when the vapor pressure of the solvent is high, but in order to remove the solvent in a shorter time, it is performed under reduced pressure (for example, 0.1 Pa to 0.1 MPa). Also good.
- reduced pressure for example, 0.1 Pa to 0.1 MPa.
- an evaporator can be used to remove the solvent under reduced pressure.
- Step C the catalyst precursor composition is heat-treated to obtain an electrode catalyst.
- the temperature during this heat treatment is 500 to 1100 ° C., preferably 600 to 1050 ° C., more preferably 700 to 950 ° C.
- the temperature of the heat treatment is too higher than the above range, sintering and grain growth occur between the particles of the obtained electrode catalyst, resulting in a decrease in the specific surface area of the electrode catalyst. As a result, the processability during processing into a catalyst layer is poor. On the other hand, if the temperature of the heat treatment is too lower than the above range, an electrode catalyst having high activity cannot be obtained.
- the atmosphere for the heat treatment is preferably an inert gas atmosphere as a main component from the viewpoint of enhancing the activity of the obtained electrode catalyst.
- inert gases nitrogen, argon, and helium are preferable and nitrogen and argon are more preferable because they are relatively inexpensive and easily available.
- These inert gas may be used individually by 1 type, and may mix and use 2 or more types. These gases are generally called inert gases, but during the heat treatment in Step C, these inert gases, that is, nitrogen, argon, helium, and the like are mixed with the catalyst precursor composition. It may be reacting.
- the heat treatment is performed using nitrogen gas, argon gas or a mixed gas of nitrogen gas and argon gas, or one or more gases selected from nitrogen gas and argon gas and one or more gases selected from hydrogen gas, ammonia gas and oxygen gas.
- nitrogen gas argon gas or a mixed gas of nitrogen gas and argon gas
- one or more gases selected from nitrogen gas and argon gas and one or more gases selected from hydrogen gas, ammonia gas and oxygen gas When carried out in a mixed gas atmosphere with gas, an electrode catalyst having high catalytic performance tends to be obtained.
- the hydrogen gas concentration is, for example, 100% by volume or less, preferably 0.01 to 10% by volume, more preferably 1 to 5% by volume.
- a roll rolling mill for example, a roll rolling mill, a ball mill, a small-diameter ball mill (bead mill), a medium stirring mill, an airflow crusher, a mortar, an automatic kneading mortar, a tank crusher, a jet mill, or the like can be used.
- a mortar an automatic kneading mortar, or a batch type ball mill is preferable.
- a heat-treated product is continuously processed in a large amount, a jet mill or a continuous type ball mill is preferable, and a continuous type ball mill is used. Among these, a bead mill is more preferable.
- Dispersion media include methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, isobutyl alcohol, tert-butyl alcohol, pentaanol, 2-heptanol Alcohols such as benzyl alcohol; Ketones such as acetone, methyl ethyl ketone, methyl propyl ketone, methyl butyl ketone, methyl isobutyl ketone, methyl amyl ketone, acetonyl acetone, diethyl ketone, dipropyl ketone, diisobutyl ketone; Ethers such as tetrahydrofuran, diethylene glycol dimethyl ether, anisole, methoxytoluene, diethyl ether, dipropyl ether, dibutyl ether; Amines such as is
- the range of x is more preferably 0.15 ⁇ x ⁇ 5.0, further preferably 0.2 ⁇ x ⁇ 4.0, and particularly preferably 1.0 ⁇ x. ⁇ 3.0
- the range of y is more preferably 0.01 ⁇ y ⁇ 1.5, still more preferably 0.02 ⁇ y ⁇ 0.5, and particularly preferably 0.03 ⁇ y ⁇ 0.
- the range of z is more preferably 0.6 ⁇ z ⁇ 2.6, further preferably 0.9 ⁇ z ⁇ 2.0, and particularly preferably 1.3 ⁇ z ⁇ 1. .9.
- the catalyst includes, as the transition metal element, one transition metal element M1 selected from the group consisting of Group 4 and Group 5 elements of the periodic table, and iron, nickel, chromium, cobalt, vanadium, and manganese.
- the ratio of the number of atoms of the transition metal element M1, transition metal element M2, carbon, nitrogen and oxygen constituting the catalyst is set to the transition metal element M1: transition.
- the catalyst contains M2 as described above, the performance becomes higher.
- the preferable ranges of x, y and z are as described above, and the range of a is more preferably 0.01 ⁇ a ⁇ 0.5, and further preferably 0.02 ⁇ a. ⁇ 0.4, particularly preferably 0.05 ⁇ a ⁇ 0.3.
- the values of a, x, y and z are values measured by the method employed in the examples described later. Due to the presence of the transition metal element M2 (at least one metal element selected from iron, nickel, chromium, cobalt, vanadium and manganese, which is different from M1), the following (1) to (3) are estimated.
- M2 at least one metal element selected from iron, nickel, chromium, cobalt, vanadium and manganese, which is different from M1
- the transition metal element M2 or the compound containing the transition metal element M2 may act as a catalyst for forming a bond between the transition metal element M1 atom and the nitrogen atom when synthesizing the electrode catalyst. is there.
- transition metal element M2 or the compound containing the transition metal element M2 prevents sintering of the heat-treated product during the heat treatment in Step C. That is, a decrease in specific surface area is prevented.
- a bias of charge occurs at the site where both metal element atoms are adjacent to each other, and the transition metal element M1 is the only metal element. There may be substrate adsorption or reaction, or product desorption that cannot be achieved with an electrocatalyst.
- the catalyst of the present invention can be effectively used as a catalyst in a direct liquid fuel cell, and particularly can be effectively used as an alternative catalyst for a platinum catalyst in a direct liquid fuel cell.
- the catalyst of the present invention is particularly useful as an oxygen reduction catalyst in a direct liquid fuel cell using liquid fuel such as methanol, ethanol and formic acid.
- liquid fuel such as methanol, ethanol and formic acid.
- the catalyst of the present invention when applied as a cathode catalyst in a direct liquid fuel cell, as described above, even when the liquid fuel is present at the cathode due to crossover, it is possible to suppress a decrease in cathode potential, and oxygen reduction. It is excellent in performance and inexpensive.
- the catalyst layer for direct liquid fuel cell of the present invention preferably further contains an electron conductive substance.
- the reduction current can be further increased.
- the electron-conducting substance is considered to increase the reduction current because it causes an electrical contact for inducing an electrochemical reaction in the catalyst.
- carbon black, graphite, graphite, activated carbon, carbon nanotube, carbon nanofiber, carbon nanohorn, fullerene and the like can be used. If the particle size of the carbon is too small, it becomes difficult to form an electron conduction path, and if it is too large, the gas diffusibility of the fuel cell catalyst layer tends to decrease, or the utilization factor of the catalyst tends to decrease. A range of 10 to 1000 nm is preferable, and a range of 10 to 100 nm is more preferable.
- the conductive polymer is not particularly limited.
- polypyrrole, polyaniline, and polythiophene are preferable, and polypyrrole is more preferable.
- the polymer electrolyte is not particularly limited as long as it is generally used in a direct liquid fuel cell catalyst layer.
- a perfluorocarbon polymer having a sulfonic acid group for example, NAFION (registered trademark) (DuPont 5% NAFION (registered trademark) solution (DE521))
- a hydrocarbon polymer having a sulfonic acid group for example, NAFION (registered trademark) (DuPont 5% NAFION (registered trademark) solution (DE521)
- Compound, polymer compound doped with inorganic acid such as phosphoric acid, organic / inorganic hybrid polymer partially substituted with proton conductive functional group, proton impregnated with phosphoric acid solution or sulfuric acid aqueous solution in polymer matrix A conductor etc. are mentioned.
- NAFION registered trademark
- DuPont 5% NAFION (registered trademark) solution (DE521) is preferable.
- Examples of the method for dispersing the catalyst on the electron conductive particles as a support include air flow dispersion and dispersion in liquid. Dispersion in liquid is preferable because a catalyst and electron conductive particles dispersed in a solvent can be used directly in the liquid fuel cell catalyst layer forming step. Examples of the dispersion in the liquid include a method using an orifice contraction flow, a method using a rotating shear flow, and a method using an ultrasonic wave.
- the solvent that can be used for dispersion in the liquid is not particularly limited as long as it does not erode the catalyst or electron conductive particles and can be dispersed, but a volatile liquid organic solvent or water may be used. it can.
- the electrolyte and the dispersing agent may be further dispersed at the same time.
- the method for forming the catalyst layer for the direct liquid fuel cell is not particularly limited.
- a suspension containing the catalyst, the electron conductive particles, and the electrolyte is applied to an electrolyte membrane or a gas diffusion layer described later.
- a method is mentioned. Examples of the application method include a dipping method, a screen printing method, a roll coating method, and a spray method.
- a liquid type is directly applied to an electrolyte membrane by a transfer method.
- the method of forming the catalyst layer for fuel cells is mentioned.
- An electrode for a direct liquid fuel cell (hereinafter also simply referred to as “electrode”) of the present invention is characterized by having the catalyst layer for a direct liquid fuel cell and a porous support layer.
- the porous support layer is a layer that diffuses gas (hereinafter also referred to as “gas diffusion layer”).
- the gas diffusion layer may be anything as long as it has electron conductivity, high gas diffusibility, and high corrosion resistance.
- carbon-based porous materials such as carbon paper and carbon cloth are used.
- Aluminum foil coated with stainless steel or corrosion resistant material is used for the material and weight reduction.
- the membrane electrode assembly may be referred to as “MEA”.
- the membrane electrode assembly may be obtained by forming the electrode catalyst layer on the electrolyte membrane and / or the gas diffusion layer, and sandwiching the both surfaces of the electrolyte membrane with the gas diffusion layer with the catalyst layer inside. it can.
- it is also possible to obtain a membrane electrode assembly by using a hot press.
- the membrane electrode assembly is sandwiched between the electrode and the electrolyte membrane without using a hot press. It is also possible to obtain.
- the hot press temperature in the use of the hot press is appropriately selected depending on the components in the electrolyte membrane and / or catalyst layer to be used, but is preferably 100 to 160 ° C, more preferably 120 to 160 ° C, More preferably, the temperature is 120 to 140 ° C. If the temperature during hot pressing is less than the lower limit, bonding may be insufficient, and if it exceeds the upper limit, components in the electrolyte membrane and / or the catalyst layer may be deteriorated.
- the hot press pressure is appropriately selected depending on the components in the electrolyte membrane and / or the catalyst layer and the type of the gas diffusion layer, but is preferably 1 to 10 MPa, more preferably 1 to 6 MPa. More preferably, it is ⁇ 5 MPa. If the pressure during hot pressing is less than the lower limit, bonding may be insufficient, and if the pressure exceeds the upper limit, the porosity of the catalyst layer and the gas diffusion layer may be reduced and performance may be deteriorated. .
- a second electrode layer different from the electrode containing the direct liquid fuel cell electrode catalyst of the present invention is disposed between the electrode and the electrolyte membrane in the production of the membrane electrode assembly. It is expected that the durability of the membrane electrode assembly is increased.
- the component (hereinafter referred to as “second electrode layer component”) to be added to the second layer is not particularly limited, but is soft so as not to damage the electrolyte membrane, and has a conductive path for ions (for example, protons) and electrons. Particularly preferred are those in which is easily formed. From this viewpoint, a conductive material such as a carbon material or a conductive polymer is preferable.
- carbon material carbon black, graphite, graphite, activated carbon, carbon nanotube, carbon nanofiber, carbon nanohorn, fullerene, porous carbon, graphene and the like are preferable, and carbon black and graphite are more preferable.
- the second electrode layer can easily move protons and hardly move methanol, thereby suppressing the influence of methanol crossover and improving catalyst performance.
- the proton conductive material is not particularly limited.
- the method for disposing the second electrode layer between the electrode and the electrolyte membrane is not particularly limited.
- the second electrode layer component may be applied directly on the surface of the electrode catalyst layer using a bar coater or spray, or may be applied directly on the surface of the electrolyte membrane.
- the second electrode layer is preferably disposed between the electrode and the electrolyte membrane, such as between the cathode catalyst layer and the electrolyte membrane, or between the anode catalyst layer and the electrolyte membrane, so that the above-described effects are suitably exhibited.
- the direct liquid fuel cell of the present invention includes the membrane electrode assembly for a direct liquid fuel cell.
- the direct liquid fuel cell of the present invention has a long lifetime with little decrease in cathode potential due to fuel crossover, and is inexpensive because no expensive precious metal such as platinum is used. Therefore, it is suitable for portable devices such as personal computers and mobile phones, automobiles, and stationary fuel cell devices.
- Transition metal elements titanium, etc.: About 0.1 g of a sample was weighed on a platinum dish, and acid was added for thermal decomposition. This thermally decomposed product was fixed, diluted, and quantified by ICP-MS. 3. BET specific surface area 0.15 g of a sample was sampled, and the specific surface area was measured with a fully automatic BET specific surface area measuring device Macsorb (manufactured by Mountec Co., Ltd.). The pretreatment time and pretreatment temperature were set at 30 ° C. and 200 ° C., respectively.
- the anode catalyst ink (1) prepared in 1 above was applied to the surface of the gas diffusion layer at 80 ° C. by an automatic spray coating apparatus (manufactured by Sanei Tech Co., Ltd.). By repeating spray application, the amount of Pt—Ru-supported carbon per unit area is 1.0 mg / cm 2 , then cut into squares (5 cm 2 ), and an electrode having an anode catalyst layer (1) is obtained. Produced.
- Example 1 Catalyst production (TiFeCNO) Titanium tetraisopropoxide (made by Junsei Chemical Co., Ltd.) 5mL and acetylacetone (Junsei Chemical Co., Ltd.) 5mL are added to a solution of ethanol (Wako Pure Chemical Industries, Ltd.) 15mL and acetic acid (Wako Pure Chemical Industries, Ltd.) 5mL. A titanium-containing mixture solution was prepared while stirring at room temperature.
- TiFeCNO Titanium tetraisopropoxide (made by Junsei Chemical Co., Ltd.) 5mL and acetylacetone (Junsei Chemical Co., Ltd.) 5mL are added to a solution of ethanol (Wako Pure Chemical Industries, Ltd.) 15mL and acetic acid (Wako Pure Chemical Industries, Ltd.) 5mL.
- a titanium-containing mixture solution was prepared while stirring at room temperature.
- the titanium-containing mixture solution was slowly added to the glycine-containing mixture solution to obtain a catalyst precursor composition.
- the temperature of the hot stirrer was set to about 100 ° C. under reduced pressure in a nitrogen atmosphere, and the solvent was slowly evaporated while heating and stirring the catalyst precursor composition. After completely evaporating the solvent of the catalyst precursor composition, the catalyst precursor composition was finely and uniformly crushed in a mortar to obtain a powder.
- This powder is put into a tubular furnace, heated to 900 ° C. at a heating rate of 10 ° C./min in a mixed gas atmosphere of 4% by volume hydrogen and nitrogen, held at 900 ° C. for 1 hour, and naturally cooled to give powder ( (Hereinafter also referred to as “catalyst (1)” or “heat-treated product (1)”).
- the powder X-ray diffraction spectrum of the catalyst (1) is shown in FIG. Diffraction line peaks of titanium compound with cubic structure and titanium oxide with rutile structure were observed. Table 1 shows the component ratio of the catalyst (1) based on the results of elemental analysis. The presence of carbon, nitrogen and oxygen was confirmed. The BET specific surface area of the catalyst (1) was 172 m 2 / g.
- membrane electrode assembly for fuel cell Nafion (registered trademark) membrane (N-212, manufactured by DuPont) as an electrolyte membrane, cathode (1) as cathode electrode, and anode as reference example 1 Electrodes having the prepared anode catalyst layer (1) (hereinafter also referred to as “anode (1)”) were prepared.
- a fuel cell membrane electrode assembly (1) (hereinafter also referred to as “MEA (1)”) in which the electrolyte membrane is disposed between the cathode and the anode was produced as follows.
- the electrolyte membrane is sandwiched between the cathode (1) and the anode (1), and the cathode catalyst layer and the anode catalyst layer are in close contact with the electrolyte membrane. Say. ) (Cell area: 5 cm 2 ).
- the temperature of the single cell (1) was adjusted to 60 ° C., and aqueous methanol solutions having different concentrations (1 mol / dm 3 and 5 mol / dm 3) were supplied as fuel to the anode side at a flow rate of 3 ml / min. Further, in order to compare the influence of methanol crossover, hydrogen was supplied to the anode side as fuel instead of methanol at 100 ml / min. Oxygen was supplied to the cathode side as an oxidant at a flow rate of 100 ml / min. Under a normal pressure environment, the starting voltage of the single cell (1) at each methanol concentration was measured, and the influence of methanol crossover was evaluated. The results are shown in Table 1.
- Example 2 Preparation of second electrode layer component ink In a mixed solvent of 25 ml of isopropyl alcohol (manufactured by Wako Pure Chemical Industries) and 25 ml of ion-exchanged water, 0.444 g of carbon black (Ketjen Black EC300J, manufactured by LION) was used as a proton conductive material.
- a two-electrode layer component ink (2) was prepared.
- the cathode catalyst ink (1) was applied to the surface of the gas diffusion layer (GDL), and the cathode catalyst ink (1) was formed.
- the cathode electrode surface was coated with the second electrode layer component ink (2) at 80 ° C. by an automatic spray coating device (manufactured by Saneitec Co., Ltd.), then cut into squares (5 cm 2 ), and the second electrode layer was produced on the surface of the cathode catalyst layer (hereinafter also referred to as “cathode (2)”).
- the second electrode layer ink was applied such that the amount of the carbon black applied as the second electrode layer component was 1.0 mg per 1 cm 2 of the electrode.
- membrane electrode assembly for fuel cell Nafion (registered trademark) membrane (N-212, manufactured by DuPont) as an electrolyte membrane, cathode (2) as cathode electrode, and anode as reference example 1 Electrodes having the prepared anode catalyst layer (1) (hereinafter also referred to as “anode (1)”) were prepared.
- a fuel cell membrane electrode assembly (2) (hereinafter also referred to as “MEA (2)”) in which the electrolyte membrane is disposed between the cathode (2) and the anode (1) was produced as follows. .
- the electrolyte membrane is sandwiched between the cathode (2) and the anode (1), and the cathode catalyst layer and the anode catalyst layer are in close contact with the electrolyte membrane. Say. ) (Cell area: 5 cm 2 ).
- the single cell (2) was supplied at 60 ° C. and 5 mol / dm 3 of methanol was supplied to the anode at 3 ml / min. Oxygen was supplied to the cathode side as an oxidant at a flow rate of 100 ml / min, and current-voltage characteristics in a single cell were measured under a normal pressure environment. From the obtained current-voltage characteristic curve, the relationship between the ratio of the current value according to the number of cell operations to the initial current density at 0.30 V and the number of operations is shown in FIG. The single cell (2) having the second electrode layer showed higher initial durability than the single cell (5) of Example 4 having no second electrode layer.
- a cathode (3) produced in the same manner as in Example 1 was used, and an electrode having an anode catalyst layer (1) produced in Reference Example 1 as an anode electrode (hereinafter referred to as “anode”). (1) ") was also prepared.
- the cathode (3) is disposed on the side of the electrolyte membrane having the second electrode layer on which the second electrode layer is applied, and the anode (1) is disposed on the side without the second electrode layer.
- Membrane electrode assembly (3) (hereinafter also referred to as “MEA (3)”) was produced as follows.
- the single cell (3) was supplied at 60 ° C., and 5 mol / dm 3 of methanol was supplied to the anode at 3 ml / min. Oxygen was supplied to the cathode side as an oxidant at a flow rate of 100 ml / min, and current-voltage characteristics in a single cell were measured under a normal pressure environment. From the obtained current-voltage characteristic curve, the relationship between the ratio of the current value according to the number of cell operations to the initial current density at 0.30 V and the number of operations is shown in FIG. The single cell (3) having the second electrode layer showed higher initial durability than the single cell (5) of Example 4 having no second electrode layer.
- Example 4 Production of Fuel Cell Membrane Electrode Assembly
- Nafion (NAFION®) membrane N-212, manufactured by DuPont
- the cathode (1) was used as the cathode electrode
- the anode Electrodes having the anode catalyst layer (1) prepared in Reference Example 1 as electrodes (hereinafter also referred to as “anode (1)”) were prepared.
- a fuel cell membrane electrode assembly (5) (hereinafter also referred to as “MEA (5)”) in which the electrolyte membrane is disposed between the cathode (1) and the anode (1) was produced as follows. .
- the single cell (5) was supplied at 60 ° C., and 5 mol / dm 3 of methanol was supplied to the anode at 3 ml / min.
- Oxygen was supplied to the cathode side as an oxidant at a flow rate of 100 ml / min, and current-voltage characteristics in a single cell were measured under a normal pressure environment. From the obtained current-voltage characteristic curve, the relationship between the ratio of the current value according to the number of cell operations to the initial current density at 0.30 V and the number of operations is shown in FIG.
- the cathode catalyst ink (4) prepared in the above 1 was applied at 80 ° C. by an automatic spray coating apparatus (manufactured by Saneitec Co., Ltd.), and then square (5 cm 2 ) The electrode which has cut
- membrane electrode assembly for fuel cell Nafion (registered trademark) membrane (N-212, manufactured by DuPont) as an electrolyte membrane, cathode (4) as cathode electrode, and anode as reference example 1
- the prepared anodes (1) were prepared.
- a fuel cell membrane electrode assembly (4) (hereinafter also referred to as “MEA (4)”) in which the electrolyte membrane is disposed between the cathode and the anode was produced as follows.
- the electrolyte membrane is sandwiched between the cathode (4) and the anode (1), and the cathode catalyst layer and the anode catalyst layer are in close contact with the electrolyte membrane.
- Cell area 5 cm 2 ).
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Sustainable Development (AREA)
- Sustainable Energy (AREA)
- Organic Chemistry (AREA)
- Catalysts (AREA)
- Inert Electrodes (AREA)
Abstract
Description
しかしながら、特許文献4および非特許文献1~3に開示された触媒は、高価なパラジウム、イリジウムといった貴金属を多量に用いており、経済上不利である。非特許文献4に開示された触媒は、貴金属を用いておらず安価であるが、触媒として実用的に充分な酸素還元能が得られていないという問題点があった。
特許文献5に開示された触媒は、安価なジルコニウム(Zr)系酸化物を用いているが、触媒として実用的に充分な酸素還元能が得られていない。
特許文献6には、白金代替材料として長周期表4族、5族及び14族の元素群から選ばれる1種以上の元素の窒化物を含む酸素還元電極材料が開示されている。
また、特許文献7には、炭化物、酸化物、窒化物を混合し、真空、不活性または非酸化性雰囲気下、500~1500℃で加熱をした炭窒酸化物が開示されている。
なお、白金は、上記燃料電池用の触媒としてだけでなく、排ガス処理用触媒または有機合成用触媒としても有用であるが、白金は価格が高く、また資源量が限られているため、これらの用途においても代替可能な触媒の開発が求められていた。
(1)
少なくとも遷移金属含有化合物および窒素含有有機化合物を混合して触媒前駆体組成物を得る工程A、
前記触媒前駆体組成物を500~1100℃の温度で熱処理して電極触媒を得る工程Cを含み、
前記遷移金属含有化合物の一部または全部が、遷移金属元素として周期表第4族および第5族の元素から選ばれる少なくとも1種の遷移金属元素M1を含有する化合物であることを特徴とする直接液体型燃料電池用電極触媒の製造方法。
前記工程Aにおいて、混合が溶媒中で行われる(1)に記載の直接液体型燃料電池用電極触媒の製造方法。
前記工程Aと工程Cとの間に、前記触媒前駆体組成物から溶媒を除去する工程Bを含む(2)に記載の直接液体型燃料電池用電極触媒の製造方法。
前記遷移金属元素M1が、チタン、ジルコニウム、ニオブおよびタンタルから選ばれる少なくとも1種であることを特徴とする(1)~(3)のいずれか一項に記載の直接液体型燃料電池用電極触媒の製造方法。
前記工程Aにおいて、前記遷移金属含有化合物の溶液と、前記窒素含有有機化合物の溶液とを混合することを特徴とする(1)~(4)のいずれか一項に記載の直接液体型燃料電池用電極触媒の製造方法。
前記窒素含有有機化合物が、前記遷移金属含有化合物中の遷移金属と共にキレートを形成可能な化合物であることを特徴とする(1)~(5)のいずれか一項に記載の直接液体型燃料電池用電極触媒の製造方法。
前記工程Aにおいて、ジケトン構造を有する化合物をさらに混合することを特徴とする(1)~(6)のいずれか一項に記載の直接液体型燃料電池用電極触媒の製造方法。
(8)
前記遷移金属含有化合物の一部が、遷移金属元素として鉄、ニッケル、クロム、コバルト、バナジウムおよびマンガンから選ばれる少なくとも1種の遷移金属元素M2を含む化合物であることを特徴とする(1)~(7)のいずれか一項に記載の直接液体型燃料電池用電極触媒の製造方法。
前記遷移金属含有化合物が、金属硝酸塩、金属酸塩化物、金属含有有機化合物、金属ハロゲン化物、金属過塩素酸塩および金属次亜塩素酸塩からなる群から選ばれる1種類以上であることを特徴とする(1)~(8)のいずれか一項に記載の直接液体型燃料電池用電極触媒の製造方法。
前記遷移金属含有化合物、前記窒素含有有機化合物および前記溶媒のいずれか1つ以上の分子中に酸素を含むことと特徴とする(2)~(9)のいずれかに記載の直接液体型燃料電池用電極触媒の製造方法。
前記窒素含有有機化合物がカルボニル基を含む(10)に記載の直接液体型燃料電池用電極触媒の製造方法。
前記カルボニル基のα炭素に窒素原子が結合している(11)に記載の直接液体型燃料電池用電極触媒の製造方法。
前記工程Cにおいて、前記触媒前駆体組成物を、水素ガスを0.01~10体積%含む雰囲気中で熱処理することを特徴とする(1)~(12)のいずれか一項に記載の直接液体型燃料電池用電極触媒の製造方法。
前記工程Cが、前記触媒前駆体組成物を500~1100℃の温度で熱処理し、得られた熱処理物を解砕して電極触媒を得る工程であることを特徴とする(1)~(13)のいずれか一項に記載の直接液体型燃料電池用電極触媒の製造方法。
(1)~(14)のいずれか一項に記載の製造方法で得られた直接液体型燃料電池用電極触媒であって、該触媒を構成する遷移金属元素、炭素、窒素および酸素の原子数の比(遷移金属元素:炭素:窒素:酸素)が1:x:y:z(ただし、0<x≦7、0<y≦2、0<z≦3である。)であることを特徴とする直接液体型燃料電池用電極触媒。
(8)に記載の製造方法で得られた直接液体型燃料電池用電極触媒であって、該触媒を構成する遷移金属元素M1、遷移金属元素M2、炭素、窒素および酸素の原子数の比(遷移金属元素M1:遷移金属元素M2:炭素:窒素:酸素)が(1-a):a:x:y:z(ただし、0<a≦0.5、0<x≦7、0<y≦2、0<z≦3である。)であることを特徴とする直接液体型燃料電池用電極触媒。
(15)または(16)に記載の直接液体型燃料電池用触媒を含むことを特徴とする直接液体型燃料電池用触媒層。
さらに電子伝導性物質を含むことを特徴とする(17)に記載の直接液体型燃料電池用触媒層。
直接液体型燃料電池用触媒層と多孔質支持層とを有する直接液体型燃料電池用電極であって、前記燃料電池用触媒層が(17)または(18)に記載の直接液体型燃料電池用触媒層であることを特徴とする直接液体型燃料電池用電極。
カソードとアノードと前記カソード及び前記アノードの間に配置された電解質膜とを有する直接液体型燃料電池用膜電極接合体であって、前記カソードおよび/または前記アノードが(19)に記載の直接液体型燃料電池用電極であることを特徴とする直接液体型燃料電池用膜電極接合体。
(20)に記載の直接液体型燃料電池用膜電極接合体を備えることを特徴とする直接液体型燃料電池。
(21)に記載の直接液体型燃料電池を備えることを特徴とする携帯機器、自動車、または定置用燃料電池装置。
本発明の直接液体型燃料電池用電極触媒の製造方法は、少なくとも遷移金属含有化合物および窒素含有有機化合物を混合して触媒前駆体組成物を得る工程A、前記触媒前駆体組成物を500~1100℃の温度で熱処理して電極触媒を得る工程Cを含み、前記遷移金属含有化合物の一部または全部が、遷移金属元素として周期表第4族および第5族の元素から選ばれる少なくとも1種の遷移金属元素M1を含有する化合物であることを特徴としている。なお本明細書において、特段の事情がない限り、原子およびイオンを、厳密に区別することなく「原子」と記載する。
工程Aでは、少なくとも遷移金属含有化合物および窒素含有有機化合物を混合して触媒前駆体組成物を得る。前記混合は、溶媒中で行われることが好ましい。溶媒中で混合を行うと遷移金属含有化合物および窒素含有有機化合物を均一に混合することができるため好ましい。
手順(i):1つの容器に溶媒を準備し、そこへ前記遷移金属含有化合物および前記窒素含有有機化合物を添加し、溶解させて、これらを混合する、
手順(ii):前記遷移金属含有化合物の溶液、および前記窒素含有有機化合物の溶液を準備し、これらを混合するが挙げられる。
手順(ii'):前記第1の遷移金属含有化合物の溶液、ならびに前記第2の遷移金属含有化合物および前記窒素含有有機化合物の溶液を準備し、これらを混合することが挙げられる。
<遷移金属含有化合物>
前記遷移金属含有化合物の一部または全部は、遷移金属元素として周期表第4族および第5族の元素から選ばれる少なくとも1種の遷移金属元素M1を含有する化合物である。前記遷移金属元素M1としては、具体的にはチタン、ジルコニウム、ハフニウム、バナジウム、ニオブおよびタンタルが挙げられる。これらは、1種単独で用いてもよく2種以上を併用してもよい。
前記遷移金属含有化合物の具体例としては、
チタンテトラメトキシド、チタンテトラエトキシド、チタンテトラプロポキシド、チタンテトライソプロポキシド、チタンテトラブトキシド、チタンテトライソブトキシド、チタンテトラペントキシド、チタンテトラアセチルアセトナート、チタンオキシジアセチルアセトナート、トリス(アセチルアセトナト)第二チタン塩化物([Ti(acac)3]2[TiCl6])、四塩化チタン、三塩化チタン、オキシ塩化チタン、四臭化チタン、三臭化チタン、オキシ臭化チタン、四ヨウ化チタン、三ヨウ化チタン、オキシヨウ化チタン等のチタン化合物;
ニオブペンタメトキシド、ニオブペンタエトキシド、ニオブペンタイソプロポキシド、ニオブペンタブトキシド、ニオブペンタペントキシド、五塩化ニオブ、オキシ塩化ニオブ、五臭化ニオブ、オキシ臭化ニオブ、五ヨウ化ニオブ、オキシヨウ化ニオブ等のニオブ化合物;
ジルコニウムテトラメトキシド、ジルコニウムテトラエトキシド、ジルコニウムテトラプロポキシド、ジルコニウムテトライソプロポキシド、ジルコニウムテトラブトキシド、ジルコニウムテトライソブトキシド、ジルコニウムテトラペントキシド、ジルコニウムテトラアセチルアセトナート、四塩化ジルコニウム、オキシ塩化ジルコニウム、四臭化ジルコニウム、オキシ臭化ジルコニウム、四ヨウ化ジルコニウム、オキシヨウ化ジルコニウム等のジルコニウム化合物;
タンタルペンタメトキシド、タンタルペンタエトキシド、タンタルペンタイソプロポキシド、タンタルペンタブトキシド、タンタルペンタペントキシド、タンタルテトラエトキシアセチルアセトナート、五塩化タンタル、オキシ塩化タンタル、五臭化タンタル、オキシ臭化タンタル、五ヨウ化タンタル、オキシヨウ化タンタル等のタンタル化合物;
ハフニウムテトラメトキシド、ハフニウムテトラエトキシド、ハフニウムテトラプロポキシド、ハフニウムテトライソプロポキシド、ハフニウムテトラブトキシド、ハフニウムテトライソブトキシド、ハフニウムテトラペントキシド、ハフニウムテトラアセチルアセトナート、四塩化ハフニウム、オキシ塩化ハフニウム、臭化ハフニウム、オキシ臭化ハフニウム、ヨウ化ハフニウム、オキシヨウ化ハフニウム等のハフニウム化合物;
バナジウムオキシトリメトキシド、バナジウムオキシトリエトキシド、バナジウムオキシトリイソプロポキシド、バナジウムオキシトリブトキシド、バナジウム(III)アセチルアセトナート、バナジウム(IV)アセチルアセトナート、五塩化バナジウム、オキシ塩化バナジウム、五臭化バナジウム、オキシ臭化バナジウム、五ヨウ化バナジウム、オキシヨウ化バナジウム等のバナジウム化合物が挙げられる。これらは、1種単独で用いてもよく2種以上を併用してもよい。
チタンテトラエトキシド、四塩化チタン、オキシ塩化チタン、チタンテトライソプロポキシド、チタンテトラアセチルアセトナート、
ニオブペンタエトキシド、五塩化ニオブ、オキシ塩化ニオブ、ニオブペンタイソプロポキシド、
ジルコニウムテトラエトキシド、四塩化ジルコニウム、オキシ塩化ジルコニウム、ジルコニウムテトライソプロポキシド、ジルコニウムテトラアセチルアセトナート、
タンタルペンタメトキシド、タンタルペンタエトキシド、五塩化タンタル、オキシ塩化タンタル、タンタルペンタイソプロポキシド、およびタンタルテトラエトキシアセチルアセトナートが好ましく、チタンテトライソプロポキシド、チタンテトラアセチルアセトナート、ニオブエトキシド、ニオブイソプロポキシド、オキシ塩化ジルコニウム、ジルコニウムテトライソプロポキシド、およびタンタルペンタイソプロポキシドがさらに好ましい。
第2の遷移金属含有化合物の具体例としては、
塩化鉄(II)、塩化鉄(III)、硫酸鉄(III)、硫化鉄(II)、硫化鉄(III)、フェロシアン化カリウム、フェリシアン化カリウム、フェロシアン化アンモニウム、フェリシアン化アンモニウム、フェロシアン化鉄、硝酸鉄(II)、硝酸鉄(III)、シュウ酸鉄(II)、シュウ酸鉄(III)、リン酸鉄(II)、リン酸鉄(III)フェロセン、水酸化鉄(II)、水酸化鉄(III)、酸化鉄(II)、酸化鉄(III)、四酸化三鉄、酢酸鉄(II)、乳酸鉄(II)、クエン酸鉄(III)等の鉄化合物;
塩化ニッケル(II)、硫酸ニッケル(II)、硫化ニッケル(II)、硝酸ニッケル(II)、シュウ酸ニッケル(II)、リン酸ニッケル(II)、ニッケルセン、水酸化ニッケル(II)、酸化ニッケル(II)、酢酸ニッケル(II)、乳酸ニッケル(II)等のニッケル化合物;
塩化クロム(II)、塩化クロム(III)、硫酸クロム(III)、硫化クロム(III)、硝酸クロム(III)、シュウ酸クロム(III)、リン酸クロム(III)、水酸化クロム(III)、酸化クロム(II)、酸化クロム(III)、酸化クロム(IV)、酸化クロム(VI)、酢酸クロム(II)、酢酸クロム(III)、乳酸クロム(III)等のクロム化合物;
塩化コバルト(II)、塩化コバルト(III)、硫酸コバルト(II)、硫化コバルト(II)、硝酸コバルト(II)、硝酸コバルト(III)、シュウ酸コバルト(II)、リン酸コバルト(II)、コバルトセン、水酸化コバルト(II)、酸化コバルト(II)、酸化コバルト(III)、四酸化三コバルト、酢酸コバルト(II)、乳酸コバルト(II)等のコバルト化合物;
塩化バナジウム(II)、塩化バナジウム(III)、塩化バナジウム(IV)、オキシ硫酸バナジウム(IV)、硫化バナジウム(III)、オキシシュウ酸バナジウム(IV)、バナジウムメタロセン、酸化バナジウム(V)、酢酸バナジウム、クエン酸バナジウム等のバナジウム化合物;
塩化マンガン(II)、硫酸マンガン(II)、硫化マンガン(II)、硝酸マンガン(II)、シュウ酸マンガン(II)、水酸化マンガン(II)、酸化マンガン(II)、酸化マンガン(III)、酢酸マンガン(II)、乳酸マンガン(II)、クエン酸マンガン等のマンガン化合物が挙げられる。これらは、1種単独で用いてもよく2種以上を併用してもよい。
塩化鉄(II)、塩化鉄(III)、フェロシアン化カリウム、フェリシアン化カリウム、フェロシアン化アンモニウム、フェリシアン化アンモニウム、酢酸鉄(II)、乳酸鉄(II)、
塩化ニッケル(II)、酢酸ニッケル(II)、乳酸ニッケル(II)、
塩化クロム(II)、塩化クロム(III)、酢酸クロム(II)、酢酸クロム(III)、乳酸クロム(III)、
塩化コバルト(II)、塩化コバルト(III)、酢酸コバルト(II)、乳酸コバルト(II)、
塩化バナジウム(II)、塩化バナジウム(III)、塩化バナジウム(IV)、オキシ硫酸バナジウム(IV)、酢酸バナジウム、クエン酸バナジウム、
塩化マンガン(II)、酢酸マンガン(II)、乳酸マンガン(II)が好ましく、
塩化鉄(II)、塩化鉄(III)、フェロシアン化カリウム、フェリシアン化カリウム、フェロシアン化アンモニウム、フェリシアン化アンモニウム、酢酸鉄(II)、乳酸鉄(II)、塩化クロム(II)、塩化クロム(III)、酢酸クロム(II)、酢酸クロム(III)、乳酸クロム(III)がさらに好ましい。
前記窒素含有有機化合物としては、特に限定は無いが、前記遷移金属含有化合物中の遷移金属原子に配位可能な配位子となり得る化合物(好ましくは、単核の錯体を形成し得る化合物)が好ましく、多座配位子(好ましくは、2座配位子または3座配位子)となり得る(キレートを形成し得る)化合物がさらに好ましい。
本発明に用いる窒素含有有機化合物は、カルボニル基を含むものが好ましい。前記カルボニル基は、官能基の一部として前記窒素含有有機化合物に含まれていてもよい。カルボニル基としては、カルボキシル基またはアルデヒド基の一部として前記窒素含有有機化合物に含まれていることが好ましく、カルボキシル基として前記窒素含有有機化合物に含まれていることが好ましい。なおカルボニル基は、窒素含有有機化合物の分子中に少なくとも一つ含まれていればよく、複数含まれていてもよい。
前記窒素含有有機化合物としては例えば、アミノ酸およびアミノ酸誘導体、が挙げられる。
得られる触媒の活性が高いことから、アラニン、グリシン、リシン、メチオニン、チロシンがより好ましく、得られる触媒が極めて高い活性を示すことから、アラニン、グリシンおよびリシンが特に好ましい。
前記溶媒としては、たとえば水、アルコール類および酸類が挙げられる。アルコール類としては、エタノール、メタノール、ブタノール、プロパノールおよびエトキシエタノールが好ましく、エタノールおよびメタノールさらに好ましい。酸類としては、酢酸、硝酸(水溶液)、塩酸、リン酸水溶液およびクエン酸水溶液が好ましく、酢酸および硝酸がさらに好ましい。これらは、1種単独で用いてもよく2種以上を併用してもよい。
(工程B)
前記工程Aにおいて、溶媒を用いて混合を行った場合には通常工程Bが行われる。工程Bでは、工程Aで得られた前記触媒前駆体組成物から溶媒を除去する。
工程Cでは、前記触媒前駆体組成物を熱処理して電極触媒を得る。
この熱処理の際の温度は、500~1100℃であり、好ましくは600~1050℃であり、より好ましくは700~950℃である。
前記熱処理で得られた熱処理物は、そのまま電極触媒として使用してもよく、さらに解砕してから電極触媒として用いてもよい。なお、本明細書において、解砕、破砕等、熱処理物を細かくする操作を、特に区別せず「解砕」と表記する。解砕を行うと、得られた電極触媒を用いて電極を製造する際の加工性、および得られる電極の特性を改善できることがある。この解砕には、たとえば、ロール転動ミル、ボールミル、小径ボールミル(ビーズミル)、媒体撹拌ミル、気流粉砕機、乳鉢、自動混練乳鉢、槽解機またはジェトミルなどを用いることができる。電極触媒が少量の場合には、乳鉢、自動混練乳鉢、バッチ式のボールミルが好ましく、熱処理物を連続的に多量に処理する場合には、ジェットミル、連続式のボールミルが好ましく、連続式のボールミルの中でもビーズミルがさらに好ましい。
アセトン、メチルエチルケトン、メチルプロピルケトン、メチルブチルケトン、メチルイゾブチルケトン、メチルアミルケトン、アセトニルアセトン、ジエチルケトン、ジプロピルケトン、ジイソブチルケトンなどのケトン類;
テトラヒドロフラン、ジエチレングリコールジメチルエーテル、アニソール、メトキシトルエン、ジエチルエーテル、ジプロピルエーテル、ジブチルエーテル等のエーテル類;
イソプロピルアミン、ブチルアミン、イソブチルアミン、シクロヘキシルアミン、ジエチルアミンなどのアミン類;
蟻酸プロピル、蟻酸イソブチル、蟻酸アミル、酢酸メチル、酢酸エチル、酢酸プロピル、酢酸ブチル、酢酸イソブチル、酢酸ペンチル、酢酸イソペンチルなどのエステル類;
アセトニトリル、ジメチルホルムアミド、ジメチルアセトアミド、N-メチルピロリドン、エチレングリコール、ジエチレングリコール、プロピレングリコール等の極性溶媒が好ましい。これらは1種単独で用いてもよく、2種以上を併用してもよい。
[直接液体型燃料電池用電極触媒]
本発明の直接液体型燃料電池用電極触媒は、上述した本発明の直接液体型燃料電池用電極触媒の製造方法により製造されることを特徴としている(以下、上述した本発明の直接液体型燃料電池用電極触媒の製造方法により製造される直接液体型燃料電池用電極触媒を「触媒」ともいう)。
遷移金属元素M2(M1とは異なる、鉄、ニッケル、クロム、コバルト、バナジウムおよびマンガンより選択される少なくとも1種の金属元素)が存在することにより、以下の(1)~(3)が推定される。
(3)電極触媒中に遷移金属元素M1および遷移金属元素M2が存在することによって、双方の金属元素原子が隣接しあう部位において、電荷の偏りが生じ、金属元素として遷移金属元素M1のみを有する電極触媒ではなしえない、基質の吸着もしくは反応、または生成物の脱離が発生している可能性がある。
本発明の直接液体型燃料電池用電極触媒の製造方法によれば、比表面積の大きな直接液体型燃料電池用電極触媒が製造され、本発明の触媒のBET法で算出される比表面積は、好ましくは30~350m2/g、より好ましくは50~300m2/g、さらに好ましくは100~300m2/gである。
本発明の触媒は、直接液体型燃料電池における触媒として有効に使用することができ、特に直接液体型燃料電池における白金触媒の代替触媒として有効に使用することができる。
直接液体型燃料電池におけるカソード触媒として白金触媒を適用すると、前記液体燃料のクロスオーバーによるカソード電位の低下が生じる。結果として、直接液体型燃料電池の性能が著しく低下する。
直接液体型燃料電池用触媒層には、アノード触媒層、カソード触媒層がある。特に前記触媒は、酸素還元能が大きく、液体燃料のクロスオーバーによるカソード電位の低下を抑制することができるので、カソード触媒層に用いることが好ましい。
前記電子伝導性粒子は通常、触媒の担体として用いられる。電子伝導性粒子を構成する材料としては、炭素、導電性高分子、導電性セラミクス、金属または酸化タングステンもしくは酸化イリジウムなどの導電性無機酸化物が挙げられ、それらを単独または組み合わせて用いることができる。特に、比表面積の大きい炭素粒子単独または比表面積の大きい炭素粒子とその他の電子伝導性粒子との混合物が好ましい。すなわち直接液体型燃料電池用触媒層としては、前記触媒と、比表面積の大きい炭素粒子とを含むことが好ましい。
電子伝導性粒子を構成する材料が、炭素の場合、前記触媒と炭素との質量比(触媒:電子伝導性粒子)は、好ましくは0.5:1~1000:1であり、より好ましくは1:1~100:1であり、さらに好ましくは4:1~10:1である。
直接液体型燃料電池用触媒層の形成方法としては、特に制限はないが、たとえば、前記触媒と電子伝導性粒子と電解質とを含む懸濁液を、後述する電解質膜またはガス拡散層に塗布する方法が挙げられる。前記塗布する方法としては、ディッピング法、スクリーン印刷法、ロールコーティング法、スプレー法などが挙げられる。また、前記触媒と電子伝導性粒子と電解質とを含む懸濁液を、塗布法またはろ過法により基材に直接液体型燃料電池用触媒層を形成した後、転写法で電解質膜に直接液体型燃料電池用触媒層を形成する方法が挙げられる。
多孔質支持層とは、ガスを拡散する層(以下「ガス拡散層」とも記す。)である。ガス拡散層としては、電子伝導性を有し、ガスの拡散性が高く、耐食性の高いものであれば何であっても構わないが、一般的にはカーボンペーパー、カーボンクロスなどの炭素系多孔質材料や、軽量化のためにステンレス、耐食材を被覆したアルミニウム箔が用いられる。
本発明の直接液体型燃料電池用膜電極接合体は、カソードとアノードと前記カソード及び前記アノードの間に配置された電解質膜とを有する膜電極接合体であって、前記カソードと前記アノードのうち少なくともいずれかが、前記電極であることを特徴としている。このとき、前記カソードと前記アノードのうちいずれか1つのみが前記電極である場合に、もう一方の電極として、従来公知の直接液体型燃料電池用電極、例えば、前記複合触媒の代わりに白金担持カーボンなど白金系触媒を含む直接液体型燃料電池用電極を用いることができる。
膜電極接合体は、電解質膜および/またはガス拡散層に前記電極触媒層を形成後、該触媒層を内側として電解質膜の両面をガス拡散層で挟むことで前記膜電極接合体を得ることができる。前記膜電極接合膜の作製においては、ホットプレスを使って、膜電極接合体を得ることも可能であり、ホットプレスを使わずに前記電極と前記電解質膜を挟んで、前記膜電極接合体を得ることも可能である。
本発明の直接液体型燃料電池は、燃料のクロスオーバーによるカソード電位の低下が少なく長寿命であり、高価な白金等の貴金属を使うことがないため安価である。従ってパソコンや携帯電話のような携帯機器、自動車、または定置用燃料電池装置に好適である。
また、実施例および比較例における各種測定は、下記の方法により行った。
1.粉末X線回折
理学電機株式会社製 ロータフレックスを用いて、試料の粉末X線回折を行った。
なお、ノイズ(N)は、ベースラインの幅とした。
炭素:試料約0.1gを量り取り、堀場製作所EMIA-110で測定を行った。
窒素・酸素:試料約0.1gを量り取り、Ni-Cupに封入後、ON分析装置で測定を行った。
3.BET比表面積
試料を0.15g採取し、全自動BET比表面積測定装置 マックソーブ((株)マウンテック製)で比表面積測定を行った。前処理時間、前処理温度は、それぞれ30分、200℃に設定した。
[参考例1]単セル評価用アノード電極の作製
1. アノード用触媒インクの調製
Pt-Ru担持カーボン(TEC61E54DM、田中貴金属工業製)0.6gを純水50mlに加え、さらにプロトン伝導性材料(NAFION(登録商標);0.25g)を含有する水溶液(NAFION5%水溶液、和光純薬工業製)5gを入れて、超音波分散機(UT-106H型シャープマニファクチャリングシステム社製)で1時間混合することにより、アノード用触媒インク(1)を調製した。
ガス拡散層(カーボンペーパーTGP-H-060、東レ社製)(5cm×5cm(25cm2))を、アセトンに30秒間浸漬し、脱脂を行った。
1. 触媒の製造(TiFeCNO)
チタンテトライソプロポキシド(純正化学(株)製)5mL及びアセチルアセトン(純正化学)5mLをエタノール(和光純薬(株)製)15mLと酢酸(和光純薬(株)製)5mLとの溶液に加え、室温で攪拌しながらチタン含有混合物溶液を作成した。また、グリシン(和光純薬(株)製)2.507g及び酢酸鉄(Aldrich社製)0.153gを純水20mLに加え、室温で攪拌して完全に溶解させてグリシン含有混合物溶液を作成した。
また、元素分析結果による触媒(1)の成分比を表1に示す。炭素、窒素及び酸素の存在が確認された。 触媒(1)のBET比表面積は172m2/gであった。
イソプロピルアルコール(和光純薬工業製)25mlとイオン交換水25mlの混合溶媒に、触媒(1)を0.355gと、電子伝導性材料としてカーボンブラック(ケッチェンブラックEC300J、LION社製)を0.089gとを加え、さらにプロトン伝導性材料としてナフィオン(NAFION(登録商標)の5%水溶液(和光純薬工業製)を5.325g加え、超音波分散機(UT-106H型シャープマニファクチャリングシステム社製)で1時間混合することにより、カソード用触媒インク(1)を調製した。
ガス拡散層(カーボンペーパー(GDL24BC、SGLカーボングループ社製))(以下「GDL」とも記す。)(5cm×5cm(25cm2))の表面に、自動スプレー塗布装置(サンエイテック社製)により、80℃で、上記カソード用触媒インク(1)を塗布し、次いで正方形(5cm2)に切断し、カソード触媒層をGDL表面に有する電極(1)(以下「カソード(1)」ともいう。)を作製した。触媒インクの塗布は、触媒(1)の塗布量が電極1cm2あたり、4.0mgとなるようにした。
電解質膜としてナフィオン(NAFION(登録商標))膜(N-212、DuPont社製)を、カソード極として上記カソード(1)を、アノード極として参考例1で作製したアノード触媒層(1)を有する電極(以下「アノード(1)」ともいう。)をそれぞれ準備した。前記カソードと前記アノードとの間に前記電解質膜を配置した燃料電池用膜電極接合体(1)(以下「MEA(1)」ともいう。)を以下のように作製した。
上記単セル(1)を60℃に温度調節し、アノード側に燃料として異なる濃度(1mol/dm3および5mol/dm3)のメタノール水溶液を流量3ml/分で供給した。また、メタノールクロスオーバーの影響を比較するために、アノード側にメタノールの代わりに水素を燃料として100ml/分で供給した。カソード側に酸化剤として酸素を流量100ml/分で供給した。常圧環境下で、各メタノール濃度における単セル(1)の開始電圧を測定し、メタノールクロスオーバーの影響を評価し、その結果を表1に示した。
1. 第2電極層成分インクの作製
イソプロピルアルコール(和光純薬工業製)25mlとイオン交換水25mlの混合溶媒に、カーボンブラック(ケッチェンブラックEC300J、LION社製)を0.444gとプロトン伝導性材料としてナフィオン(NAFION(登録商標)の5%水溶液(和光純薬工業製)を5.325g加え、超音波分散機(UT-106H型シャープマニファクチャリングシステム社製)で1時間混合することにより、第2電極層成分インク(2)を調製した。
実施例1と同様の方法で、ガス拡散層(GDL)の表面に、カソード用触媒インク(1)を塗布し、該カソード用触媒インク(1)から形成されたカソード電極表面に、自動スプレー塗布装置(サンエイテック社製)により、80℃で、前記第2電極層成分インク(2)を塗布し、次いで正方形(5cm2)に切断し、第2電極層をカソード触媒層表面に有する電極(2)(以下「カソード(2)」ともいう。)を作製した。第2電極層インクの塗布は、第2電極層成分として前記カーボングラックの塗布量が電極1cm2あたり、1.0mgとなるようにした。
電解質膜としてナフィオン(NAFION(登録商標))膜(N-212、DuPont社製)を、カソード極として上記カソード(2)を、アノード極として参考例1で作製したアノード触媒層(1)を有する電極(以下「アノード(1)」ともいう。)をそれぞれ準備した。前記カソード(2)と前記アノード(1)との間に前記電解質膜を配置した燃料電池用膜電極接合体(2)(以下「MEA(2)」ともいう。)を以下のように作製した。
上記単セル(2)を60℃、アノードに5mol/dm3のメタノールを3ml/分で供給した。カソード側に酸化剤として酸素を流量100ml/分で供給し、常圧環境下で、単セルにおける電流-電圧特性を測定した。得られた電流-電圧特性曲線から、0.30Vにおける初期電流密度に対するセル運転回数による電流値との比と運転回数との関係を図2に示した。第2電極層を有する単セル(2)は第2電極層を有してない実施例4の単セル(5)より高い初期耐久性を示した。
1. 2電極層成分インクの作製
イソプロピルアルコール(和光純薬工業製)25mlとイオン交換水25mlの混合溶媒に、カーボンブラック(ケッチェンブラックEC300J、LION社製)を0.444gとプロトン伝導性材料としてナフィオン(NAFION(登録商標)の5%水溶液(和光純薬工業製)を5.325g加え、超音波分散機(UT-106H型シャープマニファクチャリングシステム社製)で1時間混合することにより、第2電極層成分インク(3)を調製した。
電解質膜であるナフィオン(NAFION(登録商標))膜(N-212、DuPont社製)(5cm×5cm(25cm2))の表面に、自動スプレー塗布装置(サンエイテック社製)により、80℃で、前記第2電極層成分インク(3)を塗布し、次いで正方形(5cm2)に切断し、第2電極層を電解質膜表面に有する膜を作製した。第2電極層インクの塗布は、第2電極層成分として前記カーボングラックの塗布量が電解質膜1cm2あたり、1.0mgとなるようにした。
カソード極としては、実施例1と同様に作製したカソード(3)を、アノード極として参考例1で作製したアノード触媒層(1)を有する電極(以下「アノード(1)」ともいう。)をそれぞれ準備した。前記カソード(3)を、前記第2電極層を有する電解質膜の第2電極層が塗布されている側に配置し、前記アノード(1)は第2電極層が無い側に配置した燃料電池用膜電極接合体(3)(以下「MEA(3)」ともいう。)を以下のように作製した。
上記単セル(3)を60℃、アノードに5mol/dm3のメタノールを3ml/分で供給した。カソード側に酸化剤として酸素を流量100ml/分で供給し、常圧環境下で、単セルにおける電流-電圧特性を測定した。得られた電流-電圧特性曲線から、0.30Vにおける初期電流密度に対するセル運転回数による電流値との比と運転回数との関係を図2に示した。第2電極層を有する単セル(3)は第2電極層を有してない実施例4の単セル(5)より高い初期耐久性を示した。
1. 燃料電池用膜電極接合体の作製
実施例1と同様に、電解質膜としてナフィオン(NAFION(登録商標))膜(N-212、DuPont社製)を、カソード極として上記カソード(1)を、アノード極として参考例1で作製したアノード触媒層(1)を有する電極(以下「アノード(1)」ともいう。)をそれぞれ準備した。前記カソード(1)と前記アノード(1)との間に前記電解質膜を配置した燃料電池用膜電極接合体(5)(以下「MEA(5)」ともいう。)を以下のように作製した。
1. カソード用触媒(Pt/C)インクの調製
Pt担持カーボン(TEC10E70TPM、田中貴金属工業製)0.6gを純水50mlに加え、さらにプロトン伝導性材料(NAFION(登録商標);0.25g)を含有する水溶液(NAFION5%水溶液、和光純薬工業製)5gを入れて、超音波分散機(UT-106H型シャープマニファクチャリングシステム社製)で1時間混合することにより、カソード用触媒インク(4)を調製した。
ガス拡散層(カーボンペーパーTGP-H-060、東レ社製)(5cm×5cm(25cm2))を、アセトンに30秒間浸漬し、脱脂を行った。
電解質膜としてナフィオン(NAFION(登録商標))膜(N-212、DuPont社製)を、カソード極として上記カソード(4)を、アノード極として参考例1で作製したアノード(1)をそれぞれ準備した。前記カソードと前記アノードとの間に前記電解質膜を配置した燃料電池用膜電極接合体(4)(以下「MEA(4)」ともいう。)を以下のように作製した。
上記単セル(3)を60℃に温度調節し、アノード側に燃料として異なる濃度(1mol/dm3および5mol/dm3)のメタノール水溶液を流量3ml/分で供給した。また、メタノールクロスオーバーの影響を比較するために、アノード側にメタノールの代わりに水素を燃料として100ml/分で供給した。カソード側に酸化剤として酸素を流量100ml/分で供給した。常圧環境下で、各メタノール濃度における単セル(3)の開始電圧を測定し、メタノールクロスオーバーの影響を評価し、その結果を表1に示した。
Claims (22)
- 少なくとも遷移金属含有化合物および窒素含有有機化合物を混合して触媒前駆体組成物を得る工程A、
前記触媒前駆体組成物を500~1100℃の温度で熱処理して電極触媒を得る工程Cを含み、
前記遷移金属含有化合物の一部または全部が、遷移金属元素として周期表第4族および第5族の元素から選ばれる少なくとも1種の遷移金属元素M1を含有する化合物であることを特徴とする直接液体型燃料電池用電極触媒の製造方法。 - 前記工程Aにおいて、混合が溶媒中で行われる請求項1に記載の直接液体型燃料電池用電極触媒の製造方法。
- 前記工程Aと工程Cとの間に、前記触媒前駆体組成物から溶媒を除去する工程Bを含む請求項2に記載の直接液体型燃料電池用電極触媒の製造方法。
- 前記遷移金属元素M1が、チタン、ジルコニウム、ニオブおよびタンタルから選ばれる少なくとも1種であることを特徴とする請求項1~3のいずれか一項に記載の直接液体型燃料電池用電極触媒の製造方法。
- 前記工程Aにおいて、前記遷移金属含有化合物の溶液と、前記窒素含有有機化合物の溶液とを混合することを特徴とする請求項1~4のいずれか一項に記載の直接液体型燃料電池用電極触媒の製造方法。
- 前記窒素含有有機化合物が、前記遷移金属含有化合物中の遷移金属と共にキレートを形成可能な化合物であることを特徴とする請求項1~5のいずれか一項に記載の直接液体型燃料電池用電極触媒の製造方法。
- 前記工程Aにおいて、ジケトン構造を有する化合物をさらに混合することを特徴とする請求項1~6のいずれか一項に記載の直接液体型燃料電池用電極触媒の製造方法。
- 前記遷移金属含有化合物の一部が、遷移金属元素として鉄、ニッケル、クロム、コバルト、バナジウムおよびマンガンから選ばれる少なくとも1種の遷移金属元素M2を含む化合物であることを特徴とする請求項1~7のいずれか一項に記載の直接液体型燃料電池用電極触媒の製造方法。
- 前記遷移金属含有化合物が、金属硝酸塩、金属酸塩化物、金属含有有機化合物、金属ハロゲン化物、金属過塩素酸塩および金属次亜塩素酸塩からなる群から選ばれる1種類以上であることを特徴とする請求項1~8のいずれか一項に記載の直接液体型燃料電池用電極触媒の製造方法。
- 前記遷移金属含有化合物、前記窒素含有有機化合物および前記溶媒のいずれか1つ以上の分子中に酸素を含むことと特徴とする請求項2~9のいずれかに記載の直接液体型燃料電池用電極触媒の製造方法。
- 前記窒素含有有機化合物がカルボニル基を含む請求項10に記載の直接液体型燃料電池用電極触媒の製造方法。
- 前記カルボニル基のα炭素に窒素原子が結合している請求項11に記載の直接液体型燃料電池用電極触媒の製造方法。
- 前記工程Cにおいて、前記触媒前駆体組成物を、水素ガスを0.01~10体積%含む雰囲気中で熱処理することを特徴とする請求項1~12のいずれか一項に記載の直接液体型燃料電池用電極触媒の製造方法。
- 前記工程Cが、前記触媒前駆体組成物を500~1100℃の温度で熱処理し、得られた熱処理物を解砕して電極触媒を得る工程であることを特徴とする請求項1~13のいずれか一項に記載の直接液体型燃料電池用電極触媒の製造方法。
- 請求項1~14のいずれか一項に記載の製造方法で得られた直接液体型燃料電池用電極触媒であって、該触媒を構成する遷移金属元素、炭素、窒素および酸素の原子数の比(遷移金属元素:炭素:窒素:酸素)が1:x:y:z(ただし、0<x≦7、0<y≦2、0<z≦3である。)であることを特徴とする直接液体型燃料電池用電極触媒。
- 請求項8に記載の製造方法で得られた直接液体型燃料電池用電極触媒であって、該触媒を構成する遷移金属元素M1、遷移金属元素M2、炭素、窒素および酸素の原子数の比(遷移金属元素M1:遷移金属元素M2:炭素:窒素:酸素)が(1-a):a:x:y:z(ただし、0<a≦0.5、0<x≦7、0<y≦2、0<z≦3である。)であることを特徴とする直接液体型燃料電池用電極触媒。
- 請求項15または16に記載の直接液体型燃料電池用触媒を含むことを特徴とする直接液体型燃料電池用触媒層。
- さらに電子伝導性物質を含むことを特徴とする請求項17に記載の直接液体型燃料電池用触媒層。
- 直接液体型燃料電池用触媒層と多孔質支持層とを有する直接液体型燃料電池用電極であって、前記燃料電池用触媒層が請求項17または18に記載の直接液体型燃料電池用触媒層であることを特徴とする直接液体型燃料電池用電極。
- カソードとアノードと前記カソード及び前記アノードの間に配置された電解質膜とを有する直接液体型燃料電池用膜電極接合体であって、前記カソードおよび/または前記アノードが請求項19に記載の直接液体型燃料電池用電極であることを特徴とする直接液体型燃料電池用膜電極接合体。
- 請求項20に記載の直接液体型燃料電池用膜電極接合体を備えることを特徴とする直接液体型燃料電池。
- 請求項21に記載の直接液体型燃料電池を備えることを特徴とする携帯機器、自動車、または定置用燃料電池装置。
Priority Applications (5)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP12821438.4A EP2744025A4 (en) | 2011-08-09 | 2012-04-05 | METHOD FOR MANUFACTURING CATALYST FOR DIRECT LIQUID FUEL CELL, CATALYST MANUFACTURED THEREBY AND APPLICATION THEREOF |
KR1020147005941A KR101627441B1 (ko) | 2011-08-09 | 2012-04-05 | 직접 액체형 연료 전지용 촉매의 제조 방법 및 상기 방법에 의해 제조된 촉매 및 그 용도 |
CN201280037435.2A CN103718358A (zh) | 2011-08-09 | 2012-04-05 | 直接液体型燃料电池用催化剂的制造方法、以及通过该方法制造的催化剂和其用途 |
US14/236,160 US9379390B2 (en) | 2011-08-09 | 2012-04-05 | Process for producing catalyst for direct-liquid fuel cell, catalyst produced by the process and uses thereof |
JP2013503313A JP5320521B2 (ja) | 2011-08-09 | 2012-04-05 | 直接液体型燃料電池用触媒の製造方法ならびに該方法により製造された触媒およびその用途 |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2011174053 | 2011-08-09 | ||
JP2011-174053 | 2011-08-09 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2013021681A1 true WO2013021681A1 (ja) | 2013-02-14 |
Family
ID=47668211
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP2012/059375 WO2013021681A1 (ja) | 2011-08-09 | 2012-04-05 | 直接液体型燃料電池用触媒の製造方法ならびに該方法により製造された触媒およびその用途 |
Country Status (6)
Country | Link |
---|---|
US (1) | US9379390B2 (ja) |
EP (1) | EP2744025A4 (ja) |
JP (1) | JP5320521B2 (ja) |
KR (1) | KR101627441B1 (ja) |
CN (1) | CN103718358A (ja) |
WO (1) | WO2013021681A1 (ja) |
Families Citing this family (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN104826629B (zh) * | 2015-04-17 | 2018-08-07 | 华南师范大学 | 一种多孔石墨烯复合催化剂的合成方法与应用 |
KR102260303B1 (ko) * | 2019-10-10 | 2021-06-03 | 전남대학교산학협력단 | 초급속연소법을 이용한 전이금속 전기화학 촉매 및 이의 합성방법 |
CN113422079B (zh) * | 2021-05-21 | 2022-09-09 | 深圳航天科技创新研究院 | 一种燃料电池催化剂的热处理控制方法 |
Citations (12)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH07324093A (ja) * | 1994-05-31 | 1995-12-12 | Tanaka Kikinzoku Kogyo Kk | トリス(アセチルアセトナト)ルテニウム(iii) の製造方法 |
JPH11144745A (ja) | 1997-11-06 | 1999-05-28 | Asahi Glass Co Ltd | 固体高分子電解質型メタノール燃料電池 |
JP2002184427A (ja) | 2000-12-12 | 2002-06-28 | Japan Science & Technology Corp | プロトン導電性物質 |
JP2003257453A (ja) | 2001-12-27 | 2003-09-12 | Toray Ind Inc | 高分子固体電解質およびその製造方法ならびにそれを用いた固体高分子型燃料電池 |
JP2003342058A (ja) | 2002-05-23 | 2003-12-03 | Sumitomo Special Metals Co Ltd | 薄膜磁気ヘッド用セラミックス基板材料 |
JP2005135752A (ja) | 2003-10-30 | 2005-05-26 | Japan Science & Technology Agency | 燃料電池用酸素還元反応触媒 |
JP2007031781A (ja) | 2005-07-27 | 2007-02-08 | Yokohama National Univ | 酸素還元電極 |
WO2007072665A1 (ja) | 2005-12-19 | 2007-06-28 | National University Corporation Yokohama National University | 直接形燃料電池用酸素還元電極 |
WO2008111570A1 (ja) * | 2007-03-09 | 2008-09-18 | Sumitomo Chemical Company, Limited | 膜-電極接合体およびこれを用いた燃料電池 |
WO2009107518A1 (ja) * | 2008-02-28 | 2009-09-03 | 昭和電工株式会社 | 触媒およびその製造方法ならびにその用途 |
WO2009119523A1 (ja) * | 2008-03-24 | 2009-10-01 | 昭和電工株式会社 | 触媒及びその製造方法ならびにその用途 |
WO2011099493A1 (ja) * | 2010-02-10 | 2011-08-18 | 昭和電工株式会社 | 燃料電池用電極触媒の製造方法、遷移金属炭窒酸化物の製造方法、燃料電池用電極触媒およびその用途 |
Family Cites Families (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1260842C (zh) * | 2002-07-09 | 2006-06-21 | 中国科学院长春应用化学研究所 | 燃料电池阴极非铂复合催化剂的制备方法 |
JP2008258152A (ja) * | 2007-03-09 | 2008-10-23 | Sumitomo Chemical Co Ltd | 膜−電極接合体およびこれを用いた燃料電池 |
-
2012
- 2012-04-05 US US14/236,160 patent/US9379390B2/en active Active
- 2012-04-05 KR KR1020147005941A patent/KR101627441B1/ko active IP Right Grant
- 2012-04-05 WO PCT/JP2012/059375 patent/WO2013021681A1/ja active Application Filing
- 2012-04-05 CN CN201280037435.2A patent/CN103718358A/zh active Pending
- 2012-04-05 JP JP2013503313A patent/JP5320521B2/ja not_active Expired - Fee Related
- 2012-04-05 EP EP12821438.4A patent/EP2744025A4/en not_active Withdrawn
Patent Citations (12)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH07324093A (ja) * | 1994-05-31 | 1995-12-12 | Tanaka Kikinzoku Kogyo Kk | トリス(アセチルアセトナト)ルテニウム(iii) の製造方法 |
JPH11144745A (ja) | 1997-11-06 | 1999-05-28 | Asahi Glass Co Ltd | 固体高分子電解質型メタノール燃料電池 |
JP2002184427A (ja) | 2000-12-12 | 2002-06-28 | Japan Science & Technology Corp | プロトン導電性物質 |
JP2003257453A (ja) | 2001-12-27 | 2003-09-12 | Toray Ind Inc | 高分子固体電解質およびその製造方法ならびにそれを用いた固体高分子型燃料電池 |
JP2003342058A (ja) | 2002-05-23 | 2003-12-03 | Sumitomo Special Metals Co Ltd | 薄膜磁気ヘッド用セラミックス基板材料 |
JP2005135752A (ja) | 2003-10-30 | 2005-05-26 | Japan Science & Technology Agency | 燃料電池用酸素還元反応触媒 |
JP2007031781A (ja) | 2005-07-27 | 2007-02-08 | Yokohama National Univ | 酸素還元電極 |
WO2007072665A1 (ja) | 2005-12-19 | 2007-06-28 | National University Corporation Yokohama National University | 直接形燃料電池用酸素還元電極 |
WO2008111570A1 (ja) * | 2007-03-09 | 2008-09-18 | Sumitomo Chemical Company, Limited | 膜-電極接合体およびこれを用いた燃料電池 |
WO2009107518A1 (ja) * | 2008-02-28 | 2009-09-03 | 昭和電工株式会社 | 触媒およびその製造方法ならびにその用途 |
WO2009119523A1 (ja) * | 2008-03-24 | 2009-10-01 | 昭和電工株式会社 | 触媒及びその製造方法ならびにその用途 |
WO2011099493A1 (ja) * | 2010-02-10 | 2011-08-18 | 昭和電工株式会社 | 燃料電池用電極触媒の製造方法、遷移金属炭窒酸化物の製造方法、燃料電池用電極触媒およびその用途 |
Non-Patent Citations (6)
Title |
---|
K.LEE; L.ZHANG; J.ZHANG: "A novel methanol-tolerant Ir-Se chalcogenide electrocatalyst for oxygen reduction", JOURNAL OF POWER SOURCES, vol. 165, no. 1, 2007, pages 108 - 113 |
K.LEE; L.ZHANG; J.ZHANG: "IrxCol-x(x=0.3-1.0) alloy electrocatalysts, catalytic activities, and methanol tolerance in oxygen reduction reaction", JOURNAL OF POWER SOURCES, vol. 170, no. 10, 2007, pages 291 - 296 |
K.LEE; O.SAVADOGO; A.ISHIHARA; S.MITSUSHIMA; N.KAMIYA; K.OTA: "Methanol-Tolerant Oxygen Reduction Electrocatalysts Based on Pd-3d Transition Metal Alloys for Direct Methanol Fuel Cells", JOURNAL OF THE ELECTROCHEMICAL SOCIETY, vol. 153, no. 1, 2006, pages A20 - A24 |
S.DOI; A.ISHIHARA; S.MITSUSHIMA; N.KAMIYA; K.OTA: "Zirconium-Based compounds for Cathode of Polymer Electrolyte Fuel Cell", JOURNAL OF THE ELECTROCHEMICAL SOCIETY, vol. 154, no. 3, 2007, pages B362 - B369 |
See also references of EP2744025A4 |
Y.LIU; A.ISHIHARA; S.MITSUSHIMA; N.KAMIYA; K.OTA: "Transition Metal Oxides as DMFC Cathodes Without Platinum", JOURNAL OF THE ELECTROCHEMICAL SOCIETY, vol. 154, no. 7, 2007, pages B664 - B669 |
Also Published As
Publication number | Publication date |
---|---|
KR101627441B1 (ko) | 2016-06-03 |
EP2744025A1 (en) | 2014-06-18 |
CN103718358A (zh) | 2014-04-09 |
EP2744025A4 (en) | 2015-07-15 |
KR20140053284A (ko) | 2014-05-07 |
JP5320521B2 (ja) | 2013-10-23 |
JPWO2013021681A1 (ja) | 2015-03-05 |
US20140170527A1 (en) | 2014-06-19 |
US9379390B2 (en) | 2016-06-28 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US9640801B2 (en) | Process for producing catalyst carrier, process for producing composite catalyst, composite catalyst, and fuel cell using same | |
JP5828766B2 (ja) | 燃料電池用電極触媒の製造方法、および、遷移金属炭窒酸化物の製造方法 | |
JP5766138B2 (ja) | 燃料電池用電極触媒の製造方法、燃料電池用電極触媒およびその用途 | |
EP2744024B1 (en) | Method for producing electrode catalyst for fuel cells | |
JP5706596B1 (ja) | 酸素還元触媒およびその用途 | |
JP6124891B2 (ja) | 膜電極接合体、およびこれを備える燃料電池 | |
JP5819280B2 (ja) | 燃料電池用電極触媒およびその用途 | |
JP5255160B1 (ja) | 燃料電池用電極触媒およびその製造方法 | |
JP5320521B2 (ja) | 直接液体型燃料電池用触媒の製造方法ならびに該方法により製造された触媒およびその用途 | |
JP2013116458A (ja) | 触媒担体の製造方法、複合触媒の製造方法、複合触媒、およびこれを用いた直接酸化型燃料電池 | |
JPWO2014010278A1 (ja) | 燃料電池の運転方法および発電装置 | |
JP5916528B2 (ja) | インク、該インクを用いて形成される電極触媒層およびその用途 | |
JP4944281B1 (ja) | 燃料電池用電極触媒の製造方法、燃料電池用電極触媒およびその用途 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
ENP | Entry into the national phase |
Ref document number: 2013503313 Country of ref document: JP Kind code of ref document: A |
|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 12821438 Country of ref document: EP Kind code of ref document: A1 |
|
WWE | Wipo information: entry into national phase |
Ref document number: 14236160 Country of ref document: US |
|
NENP | Non-entry into the national phase |
Ref country code: DE |
|
REEP | Request for entry into the european phase |
Ref document number: 2012821438 Country of ref document: EP |
|
WWE | Wipo information: entry into national phase |
Ref document number: 2012821438 Country of ref document: EP |
|
ENP | Entry into the national phase |
Ref document number: 20147005941 Country of ref document: KR Kind code of ref document: A |