JP6836828B2 - Heteropolyacid catalyst and its manufacturing method, and electrodes and batteries using this - Google Patents
Heteropolyacid catalyst and its manufacturing method, and electrodes and batteries using this Download PDFInfo
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- JP6836828B2 JP6836828B2 JP2015114452A JP2015114452A JP6836828B2 JP 6836828 B2 JP6836828 B2 JP 6836828B2 JP 2015114452 A JP2015114452 A JP 2015114452A JP 2015114452 A JP2015114452 A JP 2015114452A JP 6836828 B2 JP6836828 B2 JP 6836828B2
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- Prior art keywords
- heteropolyacid
- catalyst
- metal
- conductive material
- molybdenum
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- 239000003054 catalyst Substances 0.000 title claims description 118
- 239000011964 heteropoly acid Substances 0.000 title claims description 59
- 238000004519 manufacturing process Methods 0.000 title claims description 14
- 239000004020 conductor Substances 0.000 claims description 50
- 229910052751 metal Inorganic materials 0.000 claims description 41
- 239000002184 metal Substances 0.000 claims description 39
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 36
- 229910052760 oxygen Inorganic materials 0.000 claims description 34
- 239000001301 oxygen Substances 0.000 claims description 34
- 229910044991 metal oxide Inorganic materials 0.000 claims description 27
- 150000004706 metal oxides Chemical class 0.000 claims description 27
- 125000004429 atom Chemical group 0.000 claims description 19
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 17
- 239000002253 acid Substances 0.000 claims description 17
- 229910052750 molybdenum Inorganic materials 0.000 claims description 17
- 239000011733 molybdenum Substances 0.000 claims description 17
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 16
- 239000000203 mixture Substances 0.000 claims description 15
- 229910000476 molybdenum oxide Inorganic materials 0.000 claims description 12
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 claims description 12
- 125000005842 heteroatom Chemical group 0.000 claims description 11
- 239000011572 manganese Substances 0.000 claims description 11
- 229910052720 vanadium Inorganic materials 0.000 claims description 11
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 10
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 10
- 239000011651 chromium Substances 0.000 claims description 10
- 239000000446 fuel Substances 0.000 claims description 10
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims description 9
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 8
- 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 claims description 8
- 229910052698 phosphorus Inorganic materials 0.000 claims description 8
- 239000011574 phosphorus Substances 0.000 claims description 8
- 229910001935 vanadium oxide Inorganic materials 0.000 claims description 8
- 229910052799 carbon Inorganic materials 0.000 claims description 7
- 238000002484 cyclic voltammetry Methods 0.000 claims description 7
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 6
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 6
- 229910052804 chromium Inorganic materials 0.000 claims description 6
- 229910017052 cobalt Inorganic materials 0.000 claims description 6
- 239000010941 cobalt Substances 0.000 claims description 6
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 6
- 229910052748 manganese Inorganic materials 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 6
- 229910052759 nickel Inorganic materials 0.000 claims description 6
- 238000000634 powder X-ray diffraction Methods 0.000 claims description 6
- 239000003575 carbonaceous material Substances 0.000 claims description 3
- 229910052742 iron Inorganic materials 0.000 claims description 3
- 150000004032 porphyrins Chemical class 0.000 claims 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 38
- 230000000052 comparative effect Effects 0.000 description 32
- 238000010438 heat treatment Methods 0.000 description 28
- 239000002994 raw material Substances 0.000 description 20
- 238000006722 reduction reaction Methods 0.000 description 19
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 15
- 230000010757 Reduction Activity Effects 0.000 description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 14
- 238000002441 X-ray diffraction Methods 0.000 description 13
- 238000006243 chemical reaction Methods 0.000 description 11
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 11
- 239000008151 electrolyte solution Substances 0.000 description 9
- 239000011734 sodium Substances 0.000 description 9
- 239000000126 substance Substances 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- 230000015572 biosynthetic process Effects 0.000 description 8
- 239000010949 copper Substances 0.000 description 8
- DHRLEVQXOMLTIM-UHFFFAOYSA-N phosphoric acid;trioxomolybdenum Chemical compound O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.OP(O)(O)=O DHRLEVQXOMLTIM-UHFFFAOYSA-N 0.000 description 8
- 238000003786 synthesis reaction Methods 0.000 description 8
- 238000010304 firing Methods 0.000 description 7
- 238000004502 linear sweep voltammetry Methods 0.000 description 7
- 229910052757 nitrogen Inorganic materials 0.000 description 7
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 7
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 6
- 239000003153 chemical reaction reagent Substances 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 239000003792 electrolyte Substances 0.000 description 6
- 239000012528 membrane Substances 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- 239000010955 niobium Substances 0.000 description 6
- 229920006395 saturated elastomer Polymers 0.000 description 6
- 239000002002 slurry Substances 0.000 description 6
- 229910052708 sodium Inorganic materials 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 239000010936 titanium Substances 0.000 description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 5
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- 239000001257 hydrogen Substances 0.000 description 5
- VLAPMBHFAWRUQP-UHFFFAOYSA-L molybdic acid Chemical compound O[Mo](O)(=O)=O VLAPMBHFAWRUQP-UHFFFAOYSA-L 0.000 description 5
- 238000007254 oxidation reaction Methods 0.000 description 5
- 229910052697 platinum Inorganic materials 0.000 description 5
- 230000009467 reduction Effects 0.000 description 5
- 239000010948 rhodium Substances 0.000 description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 4
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 4
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 229910052785 arsenic Inorganic materials 0.000 description 4
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 229910052802 copper Inorganic materials 0.000 description 4
- QXYJCZRRLLQGCR-UHFFFAOYSA-N dioxomolybdenum Chemical compound O=[Mo]=O QXYJCZRRLLQGCR-UHFFFAOYSA-N 0.000 description 4
- 239000012153 distilled water Substances 0.000 description 4
- 238000002848 electrochemical method Methods 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- 229910052733 gallium Inorganic materials 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 239000011259 mixed solution Substances 0.000 description 4
- 230000001603 reducing effect Effects 0.000 description 4
- 229910052710 silicon Inorganic materials 0.000 description 4
- 239000010703 silicon Substances 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- JBQYATWDVHIOAR-UHFFFAOYSA-N tellanylidenegermanium Chemical compound [Te]=[Ge] JBQYATWDVHIOAR-UHFFFAOYSA-N 0.000 description 4
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 4
- 229910052721 tungsten Inorganic materials 0.000 description 4
- 239000010937 tungsten Substances 0.000 description 4
- IBYSTTGVDIFUAY-UHFFFAOYSA-N vanadium monoxide Chemical compound [V]=O IBYSTTGVDIFUAY-UHFFFAOYSA-N 0.000 description 4
- QIJNJJZPYXGIQM-UHFFFAOYSA-N 1lambda4,2lambda4-dimolybdacyclopropa-1,2,3-triene Chemical compound [Mo]=C=[Mo] QIJNJJZPYXGIQM-UHFFFAOYSA-N 0.000 description 3
- 229910039444 MoC Inorganic materials 0.000 description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 230000005587 bubbling Effects 0.000 description 3
- 239000006229 carbon black Substances 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 229910052732 germanium Inorganic materials 0.000 description 3
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 229910021397 glassy carbon Inorganic materials 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229910052758 niobium Inorganic materials 0.000 description 3
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 3
- 229910000510 noble metal Inorganic materials 0.000 description 3
- 239000002798 polar solvent Substances 0.000 description 3
- 230000002441 reversible effect Effects 0.000 description 3
- VSZWPYCFIRKVQL-UHFFFAOYSA-N selanylidenegallium;selenium Chemical compound [Se].[Se]=[Ga].[Se]=[Ga] VSZWPYCFIRKVQL-UHFFFAOYSA-N 0.000 description 3
- 229910052719 titanium Inorganic materials 0.000 description 3
- 238000004832 voltammetry Methods 0.000 description 3
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 2
- 229920000557 Nafion® Polymers 0.000 description 2
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 2
- 229910052796 boron Inorganic materials 0.000 description 2
- 229910052793 cadmium Inorganic materials 0.000 description 2
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 description 2
- 229910052738 indium Inorganic materials 0.000 description 2
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 150000004715 keto acids Chemical class 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- JAGQSESDQXCFCH-UHFFFAOYSA-N methane;molybdenum Chemical compound C.[Mo].[Mo] JAGQSESDQXCFCH-UHFFFAOYSA-N 0.000 description 2
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000010970 precious metal Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 229910052702 rhenium Inorganic materials 0.000 description 2
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 description 2
- 229910052703 rhodium Inorganic materials 0.000 description 2
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 238000005070 sampling Methods 0.000 description 2
- 239000011669 selenium Substances 0.000 description 2
- 238000000527 sonication Methods 0.000 description 2
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 2
- 229910052713 technetium Inorganic materials 0.000 description 2
- GKLVYJBZJHMRIY-UHFFFAOYSA-N technetium atom Chemical compound [Tc] GKLVYJBZJHMRIY-UHFFFAOYSA-N 0.000 description 2
- ZSLUVFAKFWKJRC-IGMARMGPSA-N 232Th Chemical compound [232Th] ZSLUVFAKFWKJRC-IGMARMGPSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- 229910001339 C alloy Inorganic materials 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 229910052781 Neptunium Inorganic materials 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 229910052776 Thorium Inorganic materials 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 229910052770 Uranium Inorganic materials 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- 229910021383 artificial graphite Inorganic materials 0.000 description 1
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 description 1
- 229910052790 beryllium Inorganic materials 0.000 description 1
- ATBAMAFKBVZNFJ-UHFFFAOYSA-N beryllium atom Chemical compound [Be] ATBAMAFKBVZNFJ-UHFFFAOYSA-N 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 1
- 229910052792 caesium Inorganic materials 0.000 description 1
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 150000001722 carbon compounds Chemical class 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 150000001768 cations Chemical group 0.000 description 1
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 235000013365 dairy product Nutrition 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 229910021382 natural graphite Inorganic materials 0.000 description 1
- LFNLGNPSGWYGGD-UHFFFAOYSA-N neptunium atom Chemical compound [Np] LFNLGNPSGWYGGD-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 150000004714 phosphonium salts Chemical class 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 229910052701 rubidium Inorganic materials 0.000 description 1
- IGLNJRXAVVLDKE-UHFFFAOYSA-N rubidium atom Chemical compound [Rb] IGLNJRXAVVLDKE-UHFFFAOYSA-N 0.000 description 1
- 229910052711 selenium Inorganic materials 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 description 1
- TVXXNOYZHKPKGW-UHFFFAOYSA-N sodium molybdate (anhydrous) Chemical compound [Na+].[Na+].[O-][Mo]([O-])(=O)=O TVXXNOYZHKPKGW-UHFFFAOYSA-N 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- 229910052714 tellurium Inorganic materials 0.000 description 1
- PORWMNRCUJJQNO-UHFFFAOYSA-N tellurium atom Chemical compound [Te] PORWMNRCUJJQNO-UHFFFAOYSA-N 0.000 description 1
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- -1 tungsten (W) Chemical class 0.000 description 1
- JFALSRSLKYAFGM-UHFFFAOYSA-N uranium(0) Chemical compound [U] JFALSRSLKYAFGM-UHFFFAOYSA-N 0.000 description 1
- 238000004736 wide-angle X-ray diffraction Methods 0.000 description 1
Classifications
-
- 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
Description
本発明は、ヘテロポリ酸系触媒及びその製造方法並びにこれを用いた電極及び電池に関するものである。 The present invention relates to a heteropolyacid catalyst, a method for producing the same, and an electrode and a battery using the same.
現在、多くの化学反応や次世代電池において、白金触媒等の貴金属触媒が多く使用されている。しかしながら、貴金属の埋蔵量に限りがあることや、高価であることなどが問題となっている。さらには、例えば燃料電池電極触媒として利用する場合には、いわゆるシンタリング現象による活性低下が生じてしまったり、空気電池の触媒として利用する場合には、貴金属が電解質溶液の分解等の化学反応を引き起こしてしまったりするなど、技術的な面でも解決すべき課題はまだまだ多い。このため、白金等の貴金属を使用しない貴金属代替触媒（以下、白金代替触媒ともいう。）の開発が進められている。 Currently, precious metal catalysts such as platinum catalysts are widely used in many chemical reactions and next-generation batteries. However, there are problems such as limited reserves of precious metals and high cost. Furthermore, for example, when used as a fuel cell electrode catalyst, the activity is reduced due to the so-called sintering phenomenon, and when used as an air battery catalyst, the noble metal undergoes a chemical reaction such as decomposition of an electrolyte solution. There are still many technical issues to be solved, such as causing them. For this reason, the development of a noble metal alternative catalyst that does not use a noble metal such as platinum (hereinafter, also referred to as a platinum alternative catalyst) is underway.
白金代替触媒としては、例えば、炭素に異種原子やナノ構造を導入したカーボンアロイ触媒や、複数種の金属オキソ酸からなるヘテロポリ酸などが提案されている（特許文献１）。 As the platinum alternative catalyst, for example, a carbon alloy catalyst in which a heteroatom or a nanostructure is introduced into carbon, a heteropolyacid composed of a plurality of types of metal oxo acids, and the like have been proposed (Patent Document 1).
ここで、例えば燃料電池の原理について見てみると、アノードとカソードの間に電解質膜を挟み、アノードには水素を、カソードには酸素または空気（空気中の酸素）を供給する。それによってアノード側とカソード側でそれぞれ以下の式１及び式２の電気化学反応が起こる。具体的には、アノード側では式１の反応により発生したＨ＋イオンが電解質膜を通過してカソード側に移動すると共に、電子（ｅ−）が導電回路を経由してカソード側に移動する。一方、カソード側では供給された酸素（または供給された空気中の酸素）と、電解質膜を通過して移動してきたＨ＋イオン、そして導電回路を経由して移動してきた電子が式２のとおりに反応して水が生成する。これら一連の反応によって導電回路に直流電流が発生し起電力が生じる。
アノード側： Ｈ２ → ２Ｈ＋＋２ｅ− （式１）
カソード側： Ｏ２＋４Ｈ＋＋４ｅ− → ２Ｈ２Ｏ （式２）
Here, for example, looking at the principle of a fuel cell, an electrolyte membrane is sandwiched between an anode and a cathode, hydrogen is supplied to the anode, and oxygen or air (oxygen in the air) is supplied to the cathode. As a result, the following electrochemical reactions of Formulas 1 and 2 occur on the anode side and the cathode side, respectively. Specifically, on the anode side, H + ions generated by the reaction of Equation 1 pass through the electrolyte membrane and move to the cathode side, and electrons (e − ) move to the cathode side via the conductive circuit. On the other hand, on the cathode side, the supplied oxygen (or the oxygen in the supplied air), the H + ions that have moved through the electrolyte membrane, and the electrons that have moved through the conductive circuit are as shown in Equation 2. Water is produced in response to. A direct current is generated in the conductive circuit by these series of reactions, and an electromotive force is generated.
Anode side: H 2 → 2H + + 2e − (Equation 1)
Cathode: O 2 + 4H + + 4e - → 2H 2 O ( Equation 2)
ところで、カソード側では式２の反応（４電子反応）だけでなく、下記式３のような２電子反応が起こることが知られている。
Ｏ２＋４Ｈ＋＋４ｅ− → ２Ｈ２Ｏ （式２）
Ｏ２＋２Ｈ＋＋２ｅ− → Ｈ２Ｏ２ （式３）
Ｈ２Ｏ２＋２Ｈ＋＋２ｅ− → ２Ｈ２Ｏ （式４）
By the way, it is known that not only the reaction of the formula 2 (4-electron reaction) but also the two-electron reaction of the following formula 3 occurs on the cathode side.
O 2 + 4H + + 4e - → 2H 2 O ( Equation 2)
O 2 + 2H + + 2e - → H 2 O 2 ( Equation 3)
H 2 O 2 + 2H + + 2e - → 2H 2 O ( Equation 4)
上記２電子反応（式３）が起こると過酸化水素（Ｈ２Ｏ２）が生成する。この過酸化水素は触媒や電解質膜を劣化させ、燃料電池の耐久性を低下させる一因となっていた。 When the above two-electron reaction (Equation 3) occurs, hydrogen peroxide (H 2 O 2 ) is generated. This hydrogen peroxide deteriorates the catalyst and the electrolyte membrane, and has contributed to the deterioration of the durability of the fuel cell.
一方、ヘテロポリ酸は優れた酸化触媒であることから、主として燃料電池のアノード側触媒として用いられている。このヘテロポリ酸が導電体と複合体を形成し電極材に担持された電極をカソード側の電極として使用することも提案されている（特許文献２）。しかしながら、特許文献２では、ヘテロポリ酸と導電体を単に混合することによって使用される電極において、電極を酸素とプロトン伝導体と電子伝導体と触媒とが同時に接触するような特定の構成にすることにより高い出力電圧が得られることは記載されているが、触媒単体としての性能としてはさらなる酸素還元活性の向上が求められるものであった。 On the other hand, since heteropolyacid is an excellent oxidation catalyst, it is mainly used as an anode side catalyst of a fuel cell. It has also been proposed that the heteropolyacid forms a complex with a conductor and the electrode supported on the electrode material is used as the electrode on the cathode side (Patent Document 2). However, in Patent Document 2, in an electrode used by simply mixing a heteropolyacid and a conductor, the electrode has a specific configuration in which oxygen, a proton conductor, an electron conductor, and a catalyst come into contact with each other at the same time. Although it has been described that a higher output voltage can be obtained, further improvement in oxygen reduction activity is required for the performance of the catalyst alone.
本発明は、ヘテロポリ酸及び／またはヘテロポリ酸塩と金属酸化物と導電性材料の複合体が、高い酸素還元活性を有するとともに、２電子反応により生成する過酸化水素の還元反応（式４）を促進させることによって水にまで還元する新規触媒、およびその製造方法、並びにこれを用いた電極及び電池を提供するものである。 In the present invention, a composite of a heteropolyacid and / or a heteropolyate, a metal oxide and a conductive material has a high oxygen reduction activity, and a reduction reaction of hydrogen peroxide generated by a two-electron reaction (formula 4) is carried out. It is an object of the present invention to provide a novel catalyst that reduces to water by accelerating, a method for producing the same, and an electrode and a battery using the catalyst.
本発明者は、例えば、ヘテロポリ酸及び／またはヘテロポリ酸塩と導電性材料とを混合することにより混合物を得、それを熱処理することで、混合物中に金属酸化物が生成し、これらからなる複合体が得られること、及びこのようにして得られた複合体が、高い酸素還元活性が得られるとともに、２電子反応により生成する過酸化水素の還元反応（式４）を促進させることによって水にまで還元することを見出して本発明を完成するに至った。 The present inventor obtains a mixture by, for example, mixing a heteropolyacid and / or a heteropolylate with a conductive material, and heat-treats the mixture to form a metal oxide in the mixture, which is a composite composed of these. The body is obtained, and the complex thus obtained is added to water by obtaining high oxygen reduction activity and promoting the reduction reaction (formula 4) of hydrogen peroxide produced by the two-electron reaction. The present invention has been completed by finding that it can be reduced to.
すなわち、本発明は以下の（１）〜（１１）に関する。
（１）ヘテロポリ酸及び／またはヘテロポリ酸塩と金属酸化物と導電性材料とを含む触媒であって、前記ヘテロポリ酸及び／または前記ヘテロポリ酸塩の金属酸素酸骨格中に金属原子としてモリブデン及び／またはバナジウムを有し、および前記金属酸化物の金属原子としてモリブデン及び／またはバナジウムを有し、かつ、サイクリックボルタンメトリーにおいて、電極電位を１．０Ｖ（ｖｓ．ＲＨＥ）から０Ｖ（ｖｓ．ＲＨＥ）まで掃引した場合に、1サイクル目における、１．０Ｖ（ｖｓ．ＲＨＥ）以下、０．９Ｖ（ｖｓ．ＲＨＥ）以上の間で生じる電流密度のピーク（ｃｄＡ）と、０．９Ｖ（ｖｓ．ＲＨＥ）未満、０．７Ｖ（ｖｓ．ＲＨＥ）以上の間で生じる電流密度のピーク（ｃｄＢ）との比（ｃｄＢ／ｃｄＡ）が０超、２未満であること、を特徴とする触媒。
（２）前記金属酸化物として酸化モリブデン及び／または酸化バナジウムを含むことを特徴とする（１）に記載の触媒。
That is, the present invention relates to the following (1) to (11).
(1) A catalyst containing a heteropolyacid and / or a heteropolyate, a metal oxide, and a conductive material, and molybdenum and / or molybdenum as a metal atom in the metal oxygen acid skeleton of the heteropolyacid and / or the heteropolyate. Alternatively, it has vanadium and molybdenum and / or vanadium as the metal atom of the metal oxide, and the electrode potential is from 1.0 V (vs. RHE) to 0 V (vs. RHE) in cyclic voltammetry. When swept, the peak (cdA) of the current density generated between 1.0 V (vs. RHE) or less and 0.9 V (vs. RHE) or more in the first cycle and 0.9 V (vs. RHE) A catalyst characterized in that the ratio (cdB / cdA) to the peak (cdB) of the current density generated between less than 0.7 V (vs. RHE) and more is more than 0 and less than 2.
(2) The catalyst according to (1), which contains molybdenum oxide and / or vanadium oxide as the metal oxide.
（３）前記ヘテロポリ酸及び／または前記ヘテロポリ酸塩の金属酸素酸骨格中に金属原子としてモリブデン及びバナジウムを含むことを特徴とする（１）または（２）に記載の触媒。
（４）前記ヘテロポリ酸及び／または前記ヘテロポリ酸塩のヘテロ原子として少なくともリンを含むことを特徴とする（１）、（２）または（３）に記載の触媒。
（５）前記導電性材料が炭素材料であることを特徴とする（１）ないし（４）の何れかに記載の触媒。
(3) The catalyst according to (1) or (2), wherein molybdenum and vanadium are contained as metal atoms in the metal oxygen acid skeleton of the heteropolyacid and / or the heteropolyate.
(4) The catalyst according to (1), (2) or (3), which contains at least phosphorus as a heteroatom of the heteropolyacid and / or the heteropolyate.
(5) The catalyst according to any one of (1) to (4), wherein the conductive material is a carbon material.
（６）ヘテロポリ酸及び／またはヘテロポリ酸塩と金属酸化物と導電性材料とを含む触媒であって、粉末Ｘ線回折法における、回折角２θ＝３７．０°以上、３８．０°以下の範囲内のピーク強度（ｉＸ）と、回折角２θ＝３９．０°以上、４０．０°以下の範囲内のピーク強度（ｉＹ）との比（ｉＹ／ｉＸ）が０超、３．６未満であること、を特徴とする（１）ないし（５）の何れかに記載の触媒。
（７）ヘテロポリ酸及び／またはヘテロポリ酸塩と金属酸化物と導電性材料とを含む触媒であって、前記ヘテロポリ酸及び／またはヘテロポリ酸塩は、ケギン型構造を有すること、を特徴とする（１）ないし（６）の何れかに記載の触媒。
(6) A catalyst containing a heteropolyacid and / or a heteropolyacidate, a metal oxide, and a conductive material, which has a diffraction angle of 2θ = 37.0 ° or more and 38.0 ° or less in a powder X-ray diffraction method. The ratio (iY / iX) of the peak intensity (iX) within the range to the peak intensity (iY) within the range of diffraction angle 2θ = 39.0 ° or more and 40.0 ° or less is more than 0 and less than 3.6. The catalyst according to any one of (1) to (5).
(7) A catalyst containing a heteropolyacid and / or a heteropolylate, a metal oxide, and a conductive material, wherein the heteropolyacid and / or the heteropolylate has a kegin-type structure (7). 1) The catalyst according to any one of (6).
（８）（１）ないし（７）の何れかに記載された触媒を含むことを特徴とする電極。
（９）（８）に記載された電極を含むことを特徴とする電池。
（１０）ヘテロポリ酸及び／またはヘテロポリ酸塩と金属酸化物と導電性材料とを含む触媒の製造方法であって、金属酸素酸骨格中に金属原子としてモリブデン及び／またはバナジウムを有するヘテロポリ酸及び／またはヘテロポリ酸塩と、導電性材料とを混合し、混合物を得る工程、および前記混合物を５００℃から９００℃で熱処理する工程、を有することを特徴とする触媒の製造方法。
（１１）前記混合物を得る工程における前記ヘテロポリ酸及び／または前記ヘテロポリ酸塩の重量Ａと、前記導電性材料の重量Ｂの比Ａ／Ｂが０．００１以上１．０未満であることを特徴とする（１０）に記載の触媒の製造方法。
(8) An electrode comprising the catalyst according to any one of (1) to (7).
(9) A battery comprising the electrode according to (8).
(10) A method for producing a catalyst containing a heteropolyacid and / or a heteropolyate, a metal oxide, and a conductive material, wherein the heteropolyacid and / or vanadium has molybdenum and / or vanadium as a metal atom in the metal oxygen acid skeleton. Alternatively, a method for producing a catalyst, which comprises a step of mixing a heteropolyoxide and a conductive material to obtain a mixture, and a step of heat-treating the mixture at 500 ° C. to 900 ° C.
(11) The ratio A / B of the weight A of the heteropolyacid and / or the heteropolylate to the weight B of the conductive material in the step of obtaining the mixture is 0.001 or more and less than 1.0. The method for producing a catalyst according to (10).
なお、ここでサイクリックボルタンメトリーは、以下の条件で回転ディスク電極を用いることで得たものである。
電解液： ０．５ｍоｌ／Ｌ Ｈ２ＳＯ４水溶液（窒素ガス飽和）
温度： ２５℃
対極： ガラス状炭素
参照極： 可逆水素電極
走査範囲： １．０〜０．０Ｖ（ｖｓ．ＲＨＥ）
走査速度： ５０ｍＶ／ｓ
Here, cyclic voltammetry was obtained by using a rotating disc electrode under the following conditions.
Electrolyte: 0.5 mL / L H 2 SO 4 aqueous solution (nitrogen gas saturation)
Temperature: 25 ° C
Counter electrode: Glassy carbon Reference electrode: Reversible hydrogen electrode Scanning range: 1.0 to 0.0 V (vs. RHE)
Scanning speed: 50 mV / s
また、上記の粉末Ｘ線回折測定による回折ピーク強度は以下の条件で測定を行ったものである。
入射Ｘ線： ＣｕＫα
印加電圧： ４０ｋＶ
印加電流： ３０ｍＡ
サンプリング間隔： ０．１°
計数時間： １６秒
測定角度範囲（２θ）： ５〜９０°
The diffraction peak intensity by the above powder X-ray diffraction measurement was measured under the following conditions.
Incident X-ray: CuKα
Applied voltage: 40kV
Applied current: 30mA
Sampling interval: 0.1 °
Counting time: 16 seconds Measurement angle range (2θ): 5 to 90 °
本発明によれば、ヘテロポリ酸及び／またはヘテロポリ酸塩と導電性材料を金属酸化物と組み合わせることにより、高い酸素還元活性が得られるとともに、２電子反応により生成する過酸化水素の還元反応を促進させることによって、水にまで還元する触媒を得ることができるから、長期にわたって安定的に高い酸素還元活性を維持することができるだけでなく、電極、電解質膜等の燃料電池部材の劣化を抑制することができ、ひいては触媒の耐久性の向上、電極や燃料電池の耐久性の向上を図ることができる。 According to the present invention, by combining a heteropolyacid and / or a heteropolyate and a conductive material with a metal oxide, high oxygen reduction activity can be obtained and the reduction reaction of hydrogen peroxide generated by a two-electron reaction is promoted. By doing so, a catalyst that reduces to water can be obtained, so that not only can a high oxygen reduction activity be stably maintained for a long period of time, but also deterioration of fuel cell members such as electrodes and electrolyte membranes can be suppressed. As a result, the durability of the catalyst can be improved, and the durability of the electrodes and the fuel cell can be improved.
[ヘテロポリ酸］
ヘテロポリ酸とは、オキソ酸が重縮合したポリ酸の金属酸素酸骨格に対してヘテロ原子（hetero atom）が挿入されたポリ酸である。ヘテロポリ酸は金属原子（アデンダ原子）であるタングステン（Ｗ）、モリブデン（Ｍｏ）、バナジウム（Ｖ）等の金属からなるイソポリ酸骨格に、ヘテロ原子であるケイ素（Ｓｉ）、リン（Ｐ）、ヒ素（Ａｓ）等を含む構造を有する。具体的には以下の構造式であらわされる化合物である。
ＨxＡy［Ｍ１ａＭ２ｂＯｃ］・ｚＨ２Ｏ
Ａ：陽イオン原子
Ｍ１：ヘテロ原子
Ｍ２：金属原子（アデンダ原子）
ａ、ｂ、ｃ：定数
ｘ、ｙ、ｚ：定数
[Heteropoly acid]
A heteropolyacid is a polyacid in which a hetero atom is inserted into the metal oxygen acid skeleton of a polyacid in which an oxo acid is polycondensed. Heteropolyacid is an isopolyacid skeleton composed of metals such as tungsten (W), molybdenum (Mo), and vanadium (V), which are metal atoms (adender atoms), and silicon (Si), phosphorus (P), and arsenic, which are heteroatoms. It has a structure including (As) and the like. Specifically, it is a compound represented by the following structural formula.
H x A y [M1 a M2 b O c ] · zH 2 O
A: Cation atom M1: Heteroatom M2: Metal atom (Adenda atom)
a, b, c: constant
x, y, z: constant
ヘテロポリ酸及び／またはヘテロポリ酸塩は、例えば、モリブデン（Ｍｏ）、タングステン（Ｗ）、ニオブ（Ｎｂ）、バナジウム（Ｖ）から選ばれるアデンダ原子（addenda atom）を単数、又は複数有するもの、またはモリブデン（Ｍｏ）、タングステン（Ｗ）、ニオブ（Ｎｂ）、バナジウム（Ｖ）から選ばれるアデンダ原子を有し、アデンダ原子の一部がチタン（Ｔｉ）、クロム（Ｃｒ）、マンガン（Ｍｎ）、鉄（Ｆｅ）、コバルト（Ｃｏ）、ニッケル（Ｎｉ）、銅（Ｃｕ）、亜鉛（Ｚｎ）、ガリウム（Ｇａ）、ジルコニウム（Ｚｒ）、テクネチウム（Ｔｃ）、ロジウム（Ｒｈ）、カドミウム（Ｃｄ）、インジウム（Ｉｎ）、スズ（Ｓｎ）、タンタル（Ｔａ）、レニウム（Ｒｅ）、タリウム（Ｔｌ）、鉛（Ｐｂ）から選ばれる少なくとも何れかの原子で置換されたものであってもよい。 Heteropolyacids and / or heteropolyates have, for example, one or more addenda atoms selected from molybdenum (Mo), tungsten (W), niobium (Nb), vanadium (V), or molybdenum. It has an adender atom selected from (Mo), tungsten (W), niobium (Nb), and vanadium (V), and some of the adender atoms are titanium (Ti), chromium (Cr), manganese (Mn), and iron (Mn). Fe), cobalt (Co), nickel (Ni), copper (Cu), zinc (Zn), gallium (Ga), zirconium (Zr), technetium (Tc), rhodium (Rh), cadmium (Cd), indium ( It may be substituted with at least one atom selected from In), tin (Sn), tantalum (Ta), renium (Re), tallium (Tl), and lead (Pb).
また、ヘテロポリ酸及び／またはヘテロポリ酸塩が、例えば、ホウ素（Ｂ）、アルミニウム（Ａｌ）、ケイ素（Ｓｉ）、リン（Ｐ）、クロム（Ｃｒ）、マンガン（Ｍｎ）、鉄（Ｆｅ）、コバルト（Ｃｏ）、ニッケル（Ｎｉ）、銅（Ｃｕ）、亜鉛（Ｚｎ）、ゲルマニウム（Ｇｅ）、ヒ素（Ａｓ）から選ばれるヘテロ原子を単数、又は複数有するもの、またはホウ素（Ｂ）、アルミニウム（Ａｌ）、ケイ素（Ｓｉ）、リン（Ｐ）、クロム（Ｃｒ）、マンガン（Ｍｎ）、鉄（Ｆｅ）、コバルト（Ｃｏ）、ニッケル（Ｎｉ）、銅（Ｃｕ）、亜鉛（Ｚｎ）、ゲルマニウム（Ｇｅ）、ヒ素（Ａｓ）から選ばれるヘテロ原子を有し、へテロ原子の一部が水素（Ｈ）、ベリリウム（Ｂｅ）、炭素（Ｃ）、ナトリウム（Ｎａ）、硫黄（Ｓ）、チタン（Ｔｉ）、バナジウム（Ｖ）、ガリウム（Ｇａ）、セレン（Ｓｅ）、ジルコニウム（Ｚｒ）、ロジウム（Ｒｈ）、スズ（Ｓｎ）、アンチモン（Ｓｂ）、テルル（Ｔｅ）、ヨウ素（Ｉ）、レニウム（Ｒｅ）、白金（Ｐｔ）、ビスマス（Ｂｉ）、セリウム（Ｃｅ）、トリウム（Ｔｈ）、ウラン（Ｕ）、ネプツニウム（Ｎｐ）から選ばれる少なくとも何れかの原子で置換されたものであってもよい。 Heteropolyacids and / or heteropolyates include, for example, boron (B), aluminum (Al), silicon (Si), phosphorus (P), chromium (Cr), manganese (Mn), iron (Fe), cobalt. Those having one or more heteroatoms selected from (Co), nickel (Ni), copper (Cu), zinc (Zn), germanium (Ge), arsenic (As), or boron (B), aluminum (Al). ), Silicon (Si), Phosphorus (P), Chromium (Cr), Manganese (Mn), Iron (Fe), Cobalt (Co), Nickel (Ni), Copper (Cu), Zinc (Zn), Germanium (Ge) ), Has a heteroatom selected from arsenic (As), and some of the heteroatoms are hydrogen (H), beryllium (Be), carbon (C), sodium (Na), sulfur (S), titanium (Ti). ), Vanadium (V), gallium (Ga), selenium (Se), zirconium (Zr), rhodium (Rh), tin (Sn), antimony (Sb), tellurium (Te), iodine (I), renium (Re). ), Platinum (Pt), bismuth (Bi), cerium (Ce), thorium (Th), uranium (U), and neptunium (Np).
また、例えば、ヘテロポリ酸及び／またはヘテロポリ酸塩としては、下記の一般式（（式Ｉ）〜（式IV））で表されるヘテロポリ酸及び／またはヘテロポリ酸塩が挙げられる。 Further, for example, examples of the heteropolyacid and / or heteropolyrate include heteropolyacids and / or heteropolylates represented by the following general formulas ((Formula I) to (Formula IV)).
（式Ｉ）
アンダーソン（Anderson）型構造：ＨxＡy［Ｍ１Ｍ２６Ｏ２４］・ｚＨ２Ｏ
（式中、ｘ、ｙおよびｚはそれぞれ０≦ｘ≦８、０≦ｙ≦８、０≦ｚ≦５０の範囲内の値である。ただし、ｘおよびｙのうち少なくとも１つは０でない。）
(Formula I)
Anderson type structure: H x A y [M1M2 6 O 24 ] · zH 2 O
(In the equation, x, y and z are values within the range of 0 ≦ x ≦ 8, 0 ≦ y ≦ 8, 0 ≦ z ≦ 50, respectively. However, at least one of x and y is not 0. )
（式II）
ケギン（Keggin）型構造：ＨxＡy［Ｍ１Ｍ２１２Ｏ４０］・ｚＨ２Ｏ
（式中、ｘ、ｙおよびｚはそれぞれ０≦ｘ≦４、０≦ｙ≦４、０≦ｚ≦５０の範囲内の値である。ただし、ｘおよびｙのうち少なくとも１つは０でない。）
(Equation II)
Keggin type structure: H x A y [M1M2 12 O 40 ] · zH 2 O
(In the equation, x, y and z are values within the range of 0 ≦ x ≦ 4, 0 ≦ y ≦ 4, 0 ≦ z ≦ 50, respectively. However, at least one of x and y is not 0. )
（式III）
ドーソン（Dawson）型構造：ＨxＡy［Ｍ１２Ｍ２１８Ｏ６２］・ｚＨ２Ｏ
（式中、ｘ、ｙおよびｚはそれぞれ０≦ｘ≦８、０≦ｙ≦８、０≦ｚ≦５０の範囲内の値である。ただし、ｘおよびｙのうち少なくとも１つは０でない。）
(Equation III)
Dawson type structure: H x A y [M1 2 M2 18 O 62 ] · zH 2 O
(In the equation, x, y and z are values within the range of 0 ≦ x ≦ 8, 0 ≦ y ≦ 8, 0 ≦ z ≦ 50, respectively. However, at least one of x and y is not 0. )
（式IV）
プレイスラー（Preyssler）型構造：ＨxＡy［Ｍ１５Ｍ２３０Ｏ１１０］・ｚＨ２Ｏ
（式中、ｘ、ｙおよびｚはそれぞれ０≦ｘ≦１５、０≦ｙ≦１５、０≦ｚ≦５０の範囲内の値である。ただし、ｘおよびｙのうち少なくとも１つは０でない。）
(Equation IV)
Preyssler type structure: H x A y [M1 5 M2 30 O 110 ] · zH 2 O
(In the equation, x, y and z are values within the range of 0 ≦ x ≦ 15, 0 ≦ y ≦ 15, 0 ≦ z ≦ 50, respectively. However, at least one of x and y is not 0. )
なお、上述の（式Ｉ）〜（式IV）中、Ａはリチウム（Ｌｉ）、ナトリウム（Ｎａ）、カリウム（Ｋ）、ルビジウム（Ｒｂ）、セシウム（Ｃｓ）、マグネシウム（Ｍｇ）、カルシウム（Ｃａ）、アルミニウム（Ａｌ）、アンモニウム（ＮＨ４）、アンモニウム塩、ホスホニウム塩を表す。Ｍ１はリン（Ｐ）、ケイ素（Ｓｉ）、ヒ素（Ａｓ）、ゲルマニウム（Ｇｅ）を表す。Ｍ２はチタン（Ｔi）、バナジウム（Ｖ）、クロム（Ｃｒ）、マンガン（Ｍｎ）、鉄（Ｆｅ）、コバルト（Ｃｏ）、ニッケル（Ｎｉ）、銅（Ｃｕ）、亜鉛（Ｚｎ）、ガリウム（Ｇａ）、ジルコニウム（Ｚｒ）、ニオブ（Ｎｂ）、モリブデン（Ｍｏ）、テクネチウム（Ｔｃ）、ロジウム（Ｒｈ）、カドミウム（Ｃｄ）、インジウム（Ｉｎ）、スズ（Ｓｎ）、タンタル（Ｔａ）、タングステン（Ｗ）、レニウム（Ｒｅ）、タリウム（Ｔｌ）から選ばれる１種以上の原子である。 In the above formulas (I) to (IV), A is lithium (Li), sodium (Na), potassium (K), rubidium (Rb), cesium (Cs), magnesium (Mg), calcium (Ca). ), Aluminum (Al), ammonium (NH 4 ), ammonium salt, phosphonium salt. M1 represents phosphorus (P), silicon (Si), arsenic (As), and germanium (Ge). M2 is titanium (Ti), vanadium (V), chromium (Cr), manganese (Mn), iron (Fe), cobalt (Co), nickel (Ni), copper (Cu), zinc (Zn), gallium (Ga). ), Zirconium (Zr), Niobium (Nb), Molybdenum (Mo), Technetium (Tc), Rhenium (Rh), Cadmium (Cd), Indium (In), Tin (Sn), Tantal (Ta), Tungsten (W) ), Rhenium (Re), and gallium (Tl).
本発明のヘテロポリ酸のアデンダ原子はモリブデン及び／またはバナジウムである。アデンダ原子がモリブデンやバナジウムであると優れた酸素還元活性を有する触媒を得ることが出来る。 The adenda atom of the heteropolyacid of the present invention is molybdenum and / or vanadium. When the adenda atom is molybdenum or vanadium, a catalyst having excellent oxygen reduction activity can be obtained.
ヘテロポリ酸としては、具体的には例えば、リンモリブデン酸、ケイモリブデン酸などのようなヘテロポリモリブデン酸、リンバナジウム酸、ケイバナジウム酸などのようなヘテロポリバナジウム酸などが挙げられる。 Specific examples of the heteropolyacid include heteropolymolybdic acid such as phosphomolybdic acid and silicate molybdic acid, and heteropolyvanadium acid such as limbanadium acid and cayvanadium acid.
ヘテロポリ酸塩としては、例えば、リンモリブデン酸ナトリウム、リンモリブデン酸アンモニウムなどのようなヘテロポリモリブデン酸塩、リンバナジウム酸ナトリウム、リンバナジウム酸アンモニウムなどのようなヘテロポリバナジウム酸塩などが挙げられる。 Examples of the heteropolymate include heteropolymolybdates such as sodium phosphomolybdate and ammonium phosphomolybate, and heteropolyvanadium salts such as sodium limbanadium and ammonium limbanadium.
また、複数種のアデンダ原子を含むヘテロポリ酸として、リンバナドモリブデン酸、リンタングトモリブデン酸、ケイタングトモリブデン酸などが挙げられる。 In addition, examples of the heteropolyacid containing a plurality of types of adenda atoms include limbanado molybdic acid, lintanguto molybdic acid, and keitangto molybdic acid.
このようなヘテロポリ酸塩としては、例えば、リンモリブデン酸ナトリウム、リンモリブデン酸アンモニウム、リンモリブデン酸トリ−テトラ−ｎ−ブチルアンモニウム塩などのようなヘテロポリモリブデン酸化合物、リンバナジウム酸ナトリウム、リンバナジウム酸アンモニウム、リンバナジウム酸トリ−テトラ−ｎ−ブチルアンモニウム塩などのようなヘテロポリバナジウム酸化合物などが挙げられる。さらに、複数のポリ酸を含む化合物として、リンタングトモリブデン酸トリ−テトラ−ｎ−アンモニウム塩などのような材料が挙げられる。 Examples of such heteropolymates include heteropolymolybdic compounds such as sodium phosphomolybate, ammonium phosphomolybate, tri-tetra-n-butylammonium salt phosphomolybate, sodium limbanadium acid, and limbanadium acid. Examples thereof include heteropolyvanadium acid compounds such as ammonium and phosphomolybanoic acid tri-tetra-n-butylammonium salt. Further, examples of the compound containing a plurality of polyacids include materials such as lintangutomolybdate tri-tetra-n-ammonium salt.
これらのヘテロポリ酸及び／またはヘテロポリ酸塩を２種類以上混合して用いてもよい。また、ヘテロポリ酸及び／またはヘテロポリ酸塩と共に、ポリ酸及び／またはポリ酸塩を用いてもよい。 Two or more kinds of these heteropolyacids and / or heteropolylates may be mixed and used. Further, a polyacid and / or a polyate may be used together with a heteropolyacid and / or a heteropolyate.
本発明においては、ケギン型構造を有するヘテロポリ酸及び／またはヘテロポリ酸塩を用いることが触媒活性、安定性の観点から望ましい。例えば、リンモリブデン酸、ケイモリブデン酸、リンバナジウム酸、ケイバナジウム酸およびこれらの塩を用いることが好ましい。 In the present invention, it is desirable to use a heteropolyacid and / or a heteropolylate having a kegin-type structure from the viewpoint of catalytic activity and stability. For example, it is preferable to use phosphomolybdic acid, silicate molybdic acid, limvanadium acid, cybanadium acid and salts thereof.
また、これらのＭｏの一部がＶで置換された複合ヘテロポリ酸（例えば、Ｈ１５−αＰＶ１２−αＭｏαＯ４０で表されるヘテロポリ酸：ただし、６＜α＜１２）も好ましい。 Further, a complex heteropolyacid in which a part of these Mo is substituted with V (for example, a heteropolyacid represented by H 15-α PV 12-α Mo α O 40 : however, 6 <α <12) is also preferable.
また、用いられるヘテロ原子は少なくともリン（Ｐ）を用いたものであることが好ましい。リン（Ｐ）に加えて、上記の段落００２１に記載のヘテロ原子を任意に含むものも好ましく用いられる。 Moreover, it is preferable that the hetero atom used is at least phosphorus (P). In addition to phosphorus (P), those optionally containing the heteroatom described in paragraph 0021 above are also preferably used.
[導電性材料]
本発明に用いることができる導電性材料としては、触媒成分を所望の分散状態で担持させるための比表面積を有し、充分な電気伝導性を有しているものであればよい。具体的には炭素系の導電性材料としてカーボンブラック、黒鉛化処理したカーボンブラック、活性炭、コークス、天然黒鉛、人造黒鉛、カーボンナノチューブ、カーボンナノホーンおよびカーボンフィブリル構造体などからなるカーボン粒子が挙げられる。
[Conductive material]
The conductive material that can be used in the present invention may be any material that has a specific surface area for supporting the catalyst component in a desired dispersed state and has sufficient electrical conductivity. Specific examples of the carbon-based conductive material include carbon particles made of carbon black, graphitized carbon black, activated carbon, coke, natural graphite, artificial graphite, carbon nanotubes, carbon nanohorns, and carbon fibril structures.
中でも、本発明に用いる導電性材料としては、優れた導電性や大きな比表面積を有する観点からカーボンブラックを用いることが好ましい。 Above all, as the conductive material used in the present invention, it is preferable to use carbon black from the viewpoint of having excellent conductivity and a large specific surface area.
また、導電性材料としては炭化スズ、炭化ケイ素などに代表される炭素化合物などを挙げることができる。その他、炭素系の材料に限られず、金属系の材料を用いることもできる。例えば、金属単体や酸化チタン、酸化スズ等の導電性金属酸化物などを用いることもできる。 Further, examples of the conductive material include carbon compounds typified by tin carbide, silicon carbide and the like. In addition, the material is not limited to carbon-based materials, and metal-based materials can also be used. For example, a simple substance of a metal or a conductive metal oxide such as titanium oxide or tin oxide can be used.
導電性材料の形状も特に制限はなく、粒状、繊維状、棒状、ウィスカー状、シート状、フィルム状、スポンジ状などの形状を用いることができる。ここで、触媒反応の進みやすさを考えると、導電性材料のうちでも比表面積の大きいものが好ましく、粒状や繊維状、ウィスカー状のものが好ましい。また導電性材料が多孔質であることも好ましい。 The shape of the conductive material is also not particularly limited, and shapes such as granular, fibrous, rod-shaped, whisker-shaped, sheet-shaped, film-shaped, and sponge-shaped can be used. Here, considering the ease of proceeding with the catalytic reaction, among the conductive materials, those having a large specific surface area are preferable, and those having a granular shape, a fibrous shape, or a whiskers shape are preferable. It is also preferable that the conductive material is porous.
導電性材料のサイズも特に制限はないが、例えば導電性材料が粒状の場合には平均粒径が２０ｎｍ〜２０μｍのものを用いるのが好ましい。 The size of the conductive material is also not particularly limited, but for example, when the conductive material is granular, it is preferable to use one having an average particle diameter of 20 nm to 20 μm.
[金属酸化物]
本発明の触媒には金属酸化物として酸化モリブデン及び／または酸化バナジウムが含まれる。例えば、本発明の触媒の製造方法によれば、ヘテロポリ酸及び／またはヘテロポリ酸塩と導電性材料との混合物を熱処理する工程により、混合物系内に金属酸化物が生成する。この場合、本発明の触媒はヘテロポリ酸及び／またはヘテロポリ酸塩に用いられる金属種と同種の金属酸化物が第三の成分として存在することになる。生成した金属酸化物は、ヘテロポリ酸及び／またはヘテロポリ酸塩成分と導電性材料と複合体を形成することで、酸素還元活性、過酸化水素還元活性を高めた触媒として作用する。
[Metal oxide]
The catalyst of the present invention contains molybdenum oxide and / or vanadium oxide as metal oxides. For example, according to the method for producing a catalyst of the present invention, a metal oxide is produced in a mixture system by a step of heat-treating a mixture of a heteropolyacid and / or a heteropolylate and a conductive material. In this case, the catalyst of the present invention contains a metal oxide of the same type as the metal species used for the heteropolyacid and / or the heteropolylate as the third component. The produced metal oxide acts as a catalyst with enhanced oxygen reduction activity and hydrogen peroxide reduction activity by forming a complex with the heteropolyacid and / or the heteropolylate component and the conductive material.
なお、本発明における金属酸化物、例えば酸化モリブデンや酸化バナジウムは上記の製造工程によって生じる金属酸化物に限定されるものではない。製造工程において、ヘテロポリ酸及び／またはヘテロポリ酸塩と導電性材料に加えて、あらかじめ金属酸化物、例えば酸化モリブデンや酸化バナジウムを混合させてから焼成してもよいし、焼成後に金属酸化物を混合してもよい。 The metal oxides in the present invention, such as molybdenum oxide and vanadium oxide, are not limited to the metal oxides produced by the above manufacturing process. In the manufacturing process, in addition to the heteropolyacid and / or the heteropolyate and the conductive material, a metal oxide such as molybdenum oxide or vanadium oxide may be mixed in advance and then fired, or the metal oxide may be mixed after firing. You may.
中でも本発明において好適に用いられる金属酸化物は、酸化モリブデンである。酸化モリブデンとしては、二酸化モリブデン、すなわち４価の酸化モリブデン（ＭｏＯ２）及び／または、三酸化モリブデン、すなわち６価の酸化モリブデン（ＭｏＯ３）その他の酸化モリブデンを意味する。 Among them, the metal oxide preferably used in the present invention is molybdenum oxide. The molybdenum oxide means molybdenum dioxide, that is, tetravalent molybdenum oxide (MoO 2 ) and / or trimolybdenum trioxide, that is, hexavalent molybdenum oxide (MoO 3 ) and other molybdenum oxides.
また本発明においては金属酸化物として酸化バナジウムが好適に用いられる。この場合、酸化バナジウムとは、五酸化二バナジウム（Ｖ２Ｏ５）や一酸化バナジウム（ＶＯ）その他の酸化バナジウムを意味する。 Further, in the present invention, vanadium oxide is preferably used as the metal oxide. In this case, vanadium oxide means vanadium pentoxide (V 2 O 5 ), vanadium monoxide (VO), and other vanadium oxide.
本実施形態に係る触媒の製造方法（以下、「本製造方法」という。）は、ヘテロポリ酸及び／またはヘテロポリ酸塩、導電性材料を含む原料を混合し、５００〜９００℃の温度で加熱処理を施すことを含む。さらには、例えば、６００℃以上８００℃以下の温度で加熱処理することでもよい。 In the method for producing a catalyst according to the present embodiment (hereinafter, referred to as "the present production method"), a raw material containing a heteropolyacid and / or a heteropolylate and a conductive material is mixed and heat-treated at a temperature of 500 to 900 ° C. Including giving. Further, for example, the heat treatment may be performed at a temperature of 600 ° C. or higher and 800 ° C. or lower.
すなわち、上述した本触媒は、ヘテロポリ酸及び／またはヘテロポリ酸塩、導電性材料を含む原料に、５００℃以上の温度で加熱処理を施すことにより得られる。さらには、例えば６００℃以上の温度で加熱処理を施すことにより得られる。また、９００℃以下の温度で加熱処理をすることでもよく、さらには８００℃以下の温度で加熱処理することでもよい。また、６００℃で加熱処理することでもよく、７００℃で加熱処理することでもよく、あるいは８００℃で加熱処理することでもよい。 That is, the above-mentioned catalyst can be obtained by subjecting a raw material containing a heteropolyacid and / or a heteropolylate and a conductive material to a heat treatment at a temperature of 500 ° C. or higher. Further, it can be obtained by subjecting it to heat treatment at a temperature of, for example, 600 ° C. or higher. Further, the heat treatment may be performed at a temperature of 900 ° C. or lower, and further, the heat treatment may be performed at a temperature of 800 ° C. or lower. Further, the heat treatment may be performed at 600 ° C., the heat treatment may be performed at 700 ° C., or the heat treatment may be performed at 800 ° C.
ヘテロポリ酸及び／またはヘテロポリ酸塩は、段落００２９〜００３２で述べたものを用いることができる。導電性材料は、段落００３７〜００４１で述べたものを用いることができる。 As the heteropolyacid and / or heteropolyrate, those described in paragraphs 0029 to 0032 can be used. As the conductive material, those described in paragraphs 0037 to 0041 can be used.
原料は、ヘテロポリ酸及び／またはヘテロポリ酸塩と導電性材料とを混合して調製する。すなわち、例えば、ヘテロポリ酸及び／またはヘテロポリ酸塩と導電性材料と溶媒（例えば、水やエタノールなどの極性溶媒）とを混合する。 The raw material is prepared by mixing a heteropolyacid and / or a heteropolylate and a conductive material. That is, for example, a heteropolyacid and / or a heteropolylate is mixed with a conductive material and a solvent (eg, a polar solvent such as water or ethanol).
より具体的に、例えば、まずヘテロポリ酸及び／またはヘテロポリ酸塩と極性溶媒とを混合して混合液を調製し、次いで、当該混合液に導電性材料を添加することにより、当該溶媒中で当該ヘテロポリ酸及び／またはヘテロポリ酸塩と当該導電性材料とを混合する。 More specifically, for example, by first mixing a heteropolyacid and / or a heteropolyate with a polar solvent to prepare a mixed solution, and then adding a conductive material to the mixed solution, the said in the solvent. Heteropolyacids and / or heteropolylates are mixed with the conductive material.
原料に含まれるヘテロポリ酸及び／またはヘテロポリ酸塩の量、及び導電性材料の量は特に限られないが、例えば、当該原料は、ヘテロポリ酸及び／またはヘテロポリ酸塩を２〜７０重量％、及び導電性材料を３０〜９８重量％含むこととしてもよく、ヘテロポリ酸及び／またはヘテロポリ酸塩を３〜６０重量％、及び導電性材料を４０〜９７重量％含むことが好ましく、ヘテロポリ酸及び／またはヘテロポリ酸塩を４〜４９重量％、及び導電性材料を５１〜９６重量％含むことがより好ましい。 The amount of the heteropolyacid and / or the heteropolyrate contained in the raw material and the amount of the conductive material are not particularly limited, but for example, the raw material contains 2 to 70% by weight of the heteropolyacid and / or the heteropolylate. It may contain 30-98% by weight of the conductive material, preferably 3-60% by weight of the heteropolyacid and / or heteropolylate, and 40-97% by weight of the conductive material, preferably the heteropolyacid and / or More preferably, it contains 4 to 49% by weight of the heteropolylate and 51 to 96% by weight of the conductive material.
原料に含まれるヘテロポリ酸及び／またはヘテロポリ酸塩の金属酸素酸骨格中の金属の量、及び導電性材料の量は特に限られないが、当該原料において、導電性材料に対する金属の重量比（すなわち、原料に含まれる導電性材料の重量に対する、当該原料に含まれる金属の重量の比）（以下、「Ｍｅｔａｌ／Ｃ比」という。）は、例えば、０．００１以上、５．０以下であってもよく、０．０１以上、１．０以下であってもよく、０．０２以上、０．４８以下であってもよい。 The amount of metal in the metal oxygen skeleton of the heteropolyacid and / or heteropolylate contained in the raw material and the amount of the conductive material are not particularly limited, but in the raw material, the weight ratio of the metal to the conductive material (that is, that is). The ratio of the weight of the metal contained in the raw material to the weight of the conductive material contained in the raw material (hereinafter referred to as “Metal / C ratio”) is, for example, 0.001 or more and 5.0 or less. It may be 0.01 or more and 1.0 or less, and may be 0.02 or more and 0.48 or less.
原料におけるＭｅｔａｌ／Ｃ比は、例えば、０．０２超、０．４８未満であることが好ましい。この場合、特に優れた活性を示す触媒を製造することができる。 The Metal / C ratio in the raw material is preferably more than 0.02 and less than 0.48, for example. In this case, a catalyst showing particularly excellent activity can be produced.
また、原料におけるＭｅｔａｌ／Ｃ比は、例えば、０．０２以上、０．４７以下であることとしてもよい。さらに、Ｍｅｔａｌ／Ｃ比が０．０２以上である場合、当該Ｍｅｔａｌ／Ｃ比は、例えば、０．４６以下であってもよく、０．４５以下であってもよく、０．４４以下であってもよく、０．４３以下であってもよい。また、Ｍｅｔａｌ／Ｃ比の上限値が上記各値である場合において、当該Ｍｅｔａｌ／Ｃ比は、例えば、０．０３以上であってもよい。 Further, the Metal / C ratio in the raw material may be, for example, 0.02 or more and 0.47 or less. Further, when the Metal / C ratio is 0.02 or more, the Metal / C ratio may be, for example, 0.46 or less, 0.45 or less, or 0.44 or less. It may be 0.43 or less. Further, when the upper limit value of the Metal / C ratio is each of the above values, the Metal / C ratio may be, for example, 0.03 or more.
原料において、原料中の金属に対する、ヘテロポリ酸及び／またはヘテロポリ酸塩に由来する金属の重量比は、例えば、０．１以上であることとしてもよく、０．８以上であることとしてもよい。 In the raw material, the weight ratio of the metal derived from the heteropolyacid and / or the heteropolylate to the metal in the raw material may be, for example, 0.1 or more, or 0.8 or more.
原料は、金属源としてヘテロポリ酸及び／またはヘテロポリ酸塩のみを含む（原料において、金属に対する、ヘテロポリ酸及び／またはヘテロポリ酸塩に由来する金属の重量比が１．０である）こととしてもよい。 The raw material may contain only the heteropolyacid and / or the heteropolyrate as the metal source (in the raw material, the weight ratio of the metal derived from the heteropolyacid and / or the heteropolylate to the metal is 1.0). ..
本製造方法においては、上述のようなヘテロポリ酸及び／またはヘテロポリ酸塩、導電性材料を含む原料に、５００〜９００℃の温度で加熱処理を施して触媒を製造する。加熱処理は、原料を５００〜９００℃の温度で保持するか、この温度範囲内で所定の温度変化を与えることにより行う。加熱処理の温度は、５００℃以上９００℃以下であれば特に限られないが、例えば、６００℃以上８００℃以下の温度が好ましい。あるいは、５００℃以上の温度、または、６００℃以上の温度で、かつ、９００℃以下の温度、または８００℃以下の温度で加熱処理することでもよい。また、６００℃で加熱処理することでもよく、７００℃で加熱処理することでもよく、あるいは８００℃で加熱処理することでもよい。 In this production method, a catalyst is produced by subjecting a raw material containing the above-mentioned heteropolyacid and / or heteropolylate and conductive material to heat treatment at a temperature of 500 to 900 ° C. The heat treatment is carried out by holding the raw material at a temperature of 500 to 900 ° C. or by giving a predetermined temperature change within this temperature range. The temperature of the heat treatment is not particularly limited as long as it is 500 ° C. or higher and 900 ° C. or lower, but for example, a temperature of 600 ° C. or higher and 800 ° C. or lower is preferable. Alternatively, the heat treatment may be performed at a temperature of 500 ° C. or higher, a temperature of 600 ° C. or higher, and a temperature of 900 ° C. or lower, or a temperature of 800 ° C. or lower. Further, the heat treatment may be performed at 600 ° C., the heat treatment may be performed at 700 ° C., or the heat treatment may be performed at 800 ° C.
加熱処理は、例えば、極性溶媒中で、ヘテロポリ酸及び／またはヘテロポリ酸塩と導電性材料とを混合して混合液を調製する場合、当該混合液の溶媒を除去して得られた組成物を加熱処理することにより行う。 In the heat treatment, for example, when a mixed solution is prepared by mixing a heteropolyacid and / or a heteropolylate and a conductive material in a polar solvent, the composition obtained by removing the solvent of the mixed solution is obtained. It is carried out by heat treatment.
加熱処理の際の昇温速度は、特に限られないが、例えば、１℃／分〜５００℃／分であることとしてもよい。加熱処理の時間（原料を５００〜９００℃の温度で処理する時間）は、特に限られないが、例えば、１分以上、１０時間以下であることとしてもよい。加熱処理は、窒素等の不活性ガスの流通下または真空条件下で行うことが好ましい。 The rate of temperature rise during the heat treatment is not particularly limited, but may be, for example, 1 ° C./min to 500 ° C./min. The heat treatment time (time for treating the raw material at a temperature of 500 to 900 ° C.) is not particularly limited, but may be, for example, 1 minute or more and 10 hours or less. The heat treatment is preferably carried out under the flow of an inert gas such as nitrogen or under vacuum conditions.
本製造方法においては、原料の加熱処理により得られた組成物を、そのまま触媒として得ることとしてもよい。また、原料の加熱処理により得られた組成物を粉砕し、触媒として使用することとしてもよい。 In this production method, the composition obtained by heat treatment of the raw material may be obtained as it is as a catalyst. Further, the composition obtained by heat treatment of the raw material may be pulverized and used as a catalyst.
次に、本実施形態に係る具体的な実施例について説明する。
［実施例１］ （ＰＭｏ／ＸＣ−０．１−６００の合成）
メノー乳鉢にリンモリブデン酸、（Ｈ３［ＰＭｏ１２Ｏ４０］・ｎＨ２Ｏ（ｎ≒３０））（日本無機化学工業株式会社製）１０．０ｍｇ、Ｖｕｌｃａｎ ＸＣ−７２Ｒ（キャボット・スペシャリティ・ケミカルズ・インク製）１００ｍｇ、エタノール（和光純薬工業株式会社製 試薬特級９９．５％）２ｍＬを加え、エタノールが揮発するまで混練し、次いで７０℃で６時間減圧乾燥を行った。
次に、０．５ｍＬ／分の窒素流通下の管状炉中、１０℃／分で昇温し、６００℃で１時間熱処理することにより、触媒ＰＭｏ／ＸＣ−０．１−６００を得た。
［実施例２］ （ＰＭｏ／ＸＣ−０．１−８００の合成）
熱処理温度を８００℃とした以外は実施例１と同様に調製し、触媒ＰＭｏ／ＸＣ−０．１−８００を得た。
［実施例３］ （ＰＶＭｏ／ＸＣ−０．１−６００の合成）
１Ｌの三ツ口フラスコに蒸留水４００ｍL、６．０５ｇのモリブデン酸二ナトリウム二水和物（Ｎａ２ＭｏＯ４・２Ｈ２Ｏ）（和光純薬工業株式会社製、試薬特級、９９％）と０．２７ｇのリン酸二水素ナトリウム（ＮａＨ２ＰＯ４）（和光純薬工業株式会社製、試薬特級、９９％）を加えて溶解させた。これに、３６％塩酸（和光純薬工業株式会社製、試薬特級）より調製した０．４Ｍ ＨＣｌ水溶液１００ｍL、０．２６ｇのバナジン酸アンモニウム（ＮＨ４ＶＯ３）（和光純薬工業株式会社製、試薬特級９９％）を加えて作製したＮＨ４ＶＯ３／ＨＣｌ溶液を添加した。ＨＣｌで溶液をｐＨ２に合わせた後、９０℃で２時間撹拌した。その後、溶液を室温まで冷却し、３ｇのテトラブチルアンモニウムブロミド（[ＣＨ３（ＣＨ２）３]４ＮＢｒ）（和光純薬工業株式会社製、試薬特級９８．０％）を加え、開口径０．１μｍのメンブレンフィルターを用いて減圧濾過し、蒸留水とエタノールでリンスし、オレンジ色のリンバナドモリブデン酸塩を得た。
リンモリブデン酸を得られたリンバナドモリブデン酸塩に変えた以外は実施例１と同様に調製し、触媒ＰＶＭｏ／ＸＣ−０．１−６００を得た。
［実施例４］ （ＰＭｏ／ＸＣ−０．０５−６００の合成）
リンモリブデン酸を５．０ｍｇ、熱処理温度を６００℃とした以外は実施例１と同様に調製し、触媒ＰＭｏ／ＸＣ−０．０５−６００を得た。
［比較例１］ （ＰＭｏ／ＸＣ−０．１の合成）
熱処理を行っていない以外は実施例１と同様に調製し、触媒ＰＭｏ／ＸＣ−０．１を得た。
［比較例２］ （ＰＭｏ／ＸＣ−０．１−１０００の合成）
熱処理温度を１０００℃とした以外は実施例１と同様に調製し、触媒ＰＭｏ／ＸＣ−０．１−１０００を得た。
［比較例３］ （ＰＭｏ／ＸＣ−０．１−４００の合成）
熱処理温度を４００℃とした以外は実施例１と同様に調製し、触媒ＰＭｏ／ＸＣ−０．１−４００を得た。
［比較例４］ （ＰＭｏ／ＸＣ−１−６００の合成）
リンモリブデン酸を１００ｍｇ、熱処理温度を６００℃とした以外は実施例１と同様に調製し、触媒ＰＭｏ／ＸＣ−１−６００を得た。
Next, a specific embodiment according to the present embodiment will be described.
[Example 1] (Synthesis of PMo / XC-0.1-600)
Phosphomolybic acid in a menor dairy pot , (H 3 [PMo 12 O 40 ], nH 2 O (n ≈ 30)) (manufactured by Nippon Inorganic Chemical Industries, Ltd.) 10.0 mg, Vulcan XC-72R (Cabot Specialty Chemicals, Inc.) 100 mg of ethanol (manufactured by Ink) and 2 mL of ethanol (special grade reagent manufactured by Wako Pure Chemical Industries, Ltd. 99.5%) were added, kneaded until the ethanol volatilized, and then dried under reduced pressure at 70 ° C. for 6 hours.
Next, the temperature was raised at 10 ° C./min and heat-treated at 600 ° C. for 1 hour in a tubular furnace under a nitrogen flow of 0.5 mL / min to obtain a catalyst PMo / XC-0.1-600.
[Example 2] (Synthesis of PMo / XC-0.1-800)
A catalyst PMo / XC-0.1-800 was obtained by preparing in the same manner as in Example 1 except that the heat treatment temperature was set to 800 ° C.
[Example 3] (Synthesis of PVMo / XC-0.1-600)
Distilled water 400mL three-necked flask 1L, molybdate disodium dihydrate 6.05g (Na 2 MoO 4 · 2H 2 O) ( Wako Pure Chemical Industries, Ltd., guaranteed reagent, 99%) and 0.27g Sodium dihydrogen phosphate (NaH 2 PO 4 ) (manufactured by Wako Pure Chemical Industries, Ltd., reagent special grade, 99%) was added and dissolved. To this, 100 mL of 0.4 M HCl aqueous solution prepared from 36% hydrochloric acid (manufactured by Wako Pure Chemical Industries, Ltd., special grade reagent), 0.26 g of ammonium vanadate (NH 4 VO 3 ) (manufactured by Wako Pure Chemical Industries, Ltd., The NH 4 VO 3 / HCl solution prepared by adding reagent special grade 99%) was added. The solution was adjusted to pH 2 with HCl and then stirred at 90 ° C. for 2 hours. Then, the solution was cooled to room temperature, 3 g of tetrabutylammonium bromide ([CH 3 (CH 2 ) 3 ] 4 NBr) (manufactured by Wako Pure Chemical Industries, Ltd., reagent special grade 98.0%) was added, and the opening diameter was 0. The mixture was filtered under reduced pressure using a 1 μm membrane filter and rinsed with distilled water and ethanol to obtain an orange limbanado molybdate.
A catalyst PVMo / XC-0.1-600 was obtained by preparing in the same manner as in Example 1 except that the phosphomolybdic acid was changed to the obtained limbanado molybdate.
[Example 4] (Synthesis of PMo / XC-0.05-600)
Preparations were carried out in the same manner as in Example 1 except that phosphomolybdic acid was 5.0 mg and the heat treatment temperature was 600 ° C. to obtain a catalyst PMo / XC-0.05-600.
[Comparative Example 1] (Synthesis of PMo / XC-0.1)
A catalyst PMo / XC-0.1 was obtained by preparing in the same manner as in Example 1 except that no heat treatment was performed.
[Comparative Example 2] (Synthesis of PMo / XC-0.1-1000)
A catalyst PMo / XC-0.1-1000 was obtained by preparing in the same manner as in Example 1 except that the heat treatment temperature was set to 1000 ° C.
[Comparative Example 3] (Synthesis of PMo / XC-0.1-400)
A catalyst PMo / XC-0.1-400 was obtained by preparing in the same manner as in Example 1 except that the heat treatment temperature was set to 400 ° C.
[Comparative Example 4] (Synthesis of PMo / XC-1-600)
Preparation was carried out in the same manner as in Example 1 except that phosphomolybdic acid was 100 mg and the heat treatment temperature was 600 ° C. to obtain a catalyst PMo / XC-1-600.
［粉末Ｘ線回折法］
上述のようにして得られた触媒を粉末Ｘ線回折法（ＸＲＤ）により分析した。すなわち、粉末状の触媒からなる試料を、ガラス試料板の凹部（２ｃｍ×２ｃｍ×厚さ０．２ｍｍ）に入れるとともにスライドガラスで押さえ、当該試料をその表面と基準面とが一致するように当該凹部に均一に充填した。次いで、この充填された試料の形態が崩れないように、ガラス試料板を広角Ｘ線回折試料台に固定した。
[Powder X-ray diffraction method]
The catalyst obtained as described above was analyzed by powder X-ray diffraction (XRD). That is, a sample made of a powdery catalyst is placed in a recess (2 cm × 2 cm × thickness 0.2 mm) of a glass sample plate and pressed with a slide glass so that the surface of the sample and the reference surface coincide with each other. The recesses were uniformly filled. Next, the glass sample plate was fixed to the wide-angle X-ray diffraction sample table so that the shape of the filled sample did not collapse.
そして、Ｘ線回折装置（Ｓｈｉｍａｚｕ ＸＲＤ−６１００、株式会社島津製作所製）を用いてＸ線回折測定を行った。Ｘ線管球への印加電圧及び電流はそれぞれ４０ｋＶ及び３０ｍＡとした。サンプリング間隔は０．１°、計数時間は１６秒、測定角度範囲（２θ）は５〜９０°とした。入射Ｘ線としてはＣｕＫαを用いた。得られたＸ線回折図形に基づき、観測されたピークの強度を求めた。 Then, X-ray diffraction measurement was performed using an X-ray diffractometer (Shimazu XRD-6100, manufactured by Shimadzu Corporation). The voltage and current applied to the X-ray tube were 40 kV and 30 mA, respectively. The sampling interval was 0.1 °, the counting time was 16 seconds, and the measurement angle range (2θ) was 5 to 90 °. CuKα was used as the incident X-ray. The intensity of the observed peak was determined based on the obtained X-ray diffraction pattern.
得られたＸ線回折図形を図１〜図８に示す。図１〜図８に示すように、粉末Ｘ線回折法において、酸化モリブデン（ＭｏＯ２）由来のピークとして、回折角２θが２５．０°〜２７．０°のピーク（ｉＸ１）、回折角２θが３７．０°〜３８．０°のピーク（ｉＸ２：このｉＸ２を単にｉＸと記載する。）、回折角２θが５３．０°〜５４．０°のピーク（ｉＸ３）が観測され、炭化モリブデン（Ｍｏ２Ｃ）由来のピークとして、回折角２θが３４．０°〜３５．０°のピーク（ｉＹ１）、回折角２θが３９．０°〜４０．０°のピーク（ｉＹ２：このｉＹ２を単にｉＹと記載する。）、回折角２θが５２．０°〜５２．９°のピーク（ｉＹ３）、回折角２θが６１．０°〜６２．０°のピーク（ｉＹ４）が観測された。 The obtained X-ray diffraction figures are shown in FIGS. 1 to 8. As shown in FIGS. 1 to 8, in the powder X-ray diffraction method, peaks having a diffraction angle 2θ of 25.0 ° to 27.0 ° (iX 1 ) and diffraction angles as peaks derived from molybdenum oxide (MoO 2). 2θ peaks of 37.0 ° ~38.0 ° (iX 2: . this iX 2 to simply as iX), the diffraction angle 2θ is 53.0 ° ~54.0 ° peak (iX 3) is observed is, as a peak derived from molybdenum carbide (Mo 2 C), the peak of the diffraction angle 2θ is 34.0 ° ~35.0 ° (iY 1) , the diffraction angle 2θ is 39.0 ° 40.0 ° peak ( iY 2 : This iY 2 is simply referred to as iY), a peak with a diffraction angle 2θ of 52.0 ° to 52.9 ° (iY 3 ), and a peak with a diffraction angle 2θ of 61.0 ° to 62.0 °. (iY 4) was observed.
一方、触媒の酸素還元活性については、表１に示されるように、焼成なしで作製した比較例１の触媒（ＰＭｏ／ＸＣ−０．１）の酸素還元活性開始電位が０．３６１（Ｖｖｓ．ＲＨＥ）であったのに対し、焼成温度６００℃で作製した実施例１、３、４の触媒、焼成温度８００℃で作製した実施例２の触媒の酸素還元活性開始電位が０．４５１（Ｖｖｓ．ＲＨＥ）〜０．４９１（Ｖｖｓ．ＲＨＥ）であった。ここで、触媒の酸素還元活性は下記の段落００７１の方法で評価した結果である。 On the other hand, regarding the oxygen reduction activity of the catalyst, as shown in Table 1, the oxygen reduction activity starting potential of the catalyst (PMo / XC-0.1) of Comparative Example 1 produced without firing was 0.361 (Vvs. The oxygen reduction activity start potential of the catalysts of Examples 1, 3 and 4 prepared at a firing temperature of 600 ° C. and the catalyst of Example 2 prepared at a firing temperature of 800 ° C. was 0.451 (Vvs). RHE) to 0.491 (Vvs.RHE). Here, the oxygen reduction activity of the catalyst is the result of evaluation by the method of paragraph 0071 below.
すなわち、実施例に係る触媒の酸素還元活性は、比較例に係る触媒のそれより高かった。特に、実施例４に係る触媒の酸素還元活性はより高かった。 That is, the oxygen reduction activity of the catalyst according to the example was higher than that of the catalyst according to the comparative example. In particular, the oxygen reduction activity of the catalyst according to Example 4 was higher.
さらに、触媒の過酸化水素還元活性については、表１に示されるように、焼成なしで作製した比較例１の触媒（ＰＭｏ／ＸＣ−０．１）の過酸化水素還元に対する０．１Ｖの時の電流密度の絶対値が６．５０×１０−２ｍＡ／ｃｍ２であったのに対し、焼成温度６００℃で作製した実施例１、３、４の触媒、焼成温度８００℃で作製した実施例２の触媒の過酸化水素還元に対する０．１Ｖの時の電流密度の絶対値が７．６３×１０−２〜１１．３×１０−２ｍＡ／ｃｍ２であった。ここで、触媒の過酸化水素還元活性は下記の段落００８２の方法で評価した結果である。 Further, regarding the hydrogen peroxide reducing activity of the catalyst, as shown in Table 1, when the catalyst (PMo / XC-0.1) of Comparative Example 1 produced without firing was 0.1 V with respect to the hydrogen peroxide reduction. The absolute value of the current density was 6.50 × 10 -2 mA / cm 2 , whereas the catalysts of Examples 1, 3 and 4 prepared at a firing temperature of 600 ° C. and the firing temperature of 800 ° C. The absolute value of the current density at 0.1 V with respect to the hydrogen peroxide reduction of the catalyst of Example 2 was 7.63 × 10 -2 to 11.3 × 10 -2 mA / cm 2 . Here, the hydrogen peroxide reducing activity of the catalyst is the result of evaluation by the method of paragraph 882 below.
すなわち、実施例に係る触媒の過酸化水素還元活性は、比較例に係る触媒のそれより高かった。特に、実施例１および４に係る触媒の過酸化水素還元活性はより高かった。 That is, the hydrogen peroxide reducing activity of the catalyst according to the example was higher than that of the catalyst according to the comparative example. In particular, the hydrogen peroxide reducing activity of the catalysts according to Examples 1 and 4 was higher.
ここで、図１〜図８に示されるＸＲＤピーク強度に着目すると、実施例１〜４に係る触媒について、回折角２θが２５．０°〜２７．０°のピーク（ｉＸ１）と３７．０°〜３８．０°のピーク（ｉＸ２、または単にｉＸ）が観測された。また、実施例１、２、４に係る触媒について、回折角２θが５３．０°〜５４．０°のピーク（ｉＸ３）が観測された。また、実施例１、２に係る触媒について、回折角２θが６１．０°〜６２．０°のピーク（ｉＹ４）が観測された。また、実施例１〜４に係る触媒について、回折角２θが３９．０°〜４０．０°のピーク（ｉＹ２または単にｉＹ）は強度の小さなものもあった。
一方、比較例２、４に係る触媒について、回折角２θが２５．０°〜２７．０°のピーク（ｉＸ１）と３７．０°〜３８．０°のピーク（ｉＸ２、または単にｉＸ）が観測された。また、比較例４に係る触媒について、回折２θが５３．０°〜５４．０°のピーク（ｉＸ３）が観測され、回折角２θが３９．０°〜４０．０°のピーク（ｉＹ２または単にｉＹ）は観測されなかった。また、比較例２に係る触媒について、回折角２θが３４．０°〜３５．０°のピーク（ｉＹ１）、回折角２θが３９．０°〜４０．０°のピーク（ｉＹ２又は単にｉＹ）、回折角２θが５２．０°〜５２．９°のピーク（ｉＹ３）、回折角２θが６１．０°〜６２．０°のピーク（ｉＹ４）が観測された。ここで、比較例２に係る触媒について、ｉＸ２は観測されるがｉＹ２の強度が大きく、ｉＹ１〜ｉＹ４が観測されることから、炭化モリブデン（Ｍｏ２Ｃ）が支配的であると考えられる。
Focusing on the XRD peak intensities shown in FIGS. 1 to 8, the catalysts according to Examples 1 to 4 have peaks (iX 1 ) having a diffraction angle of 2θ of 25.0 ° to 27.0 ° and 37. 0 ° ~38.0 ° peak (iX 2 or simply iX,) was observed. Further, for the catalysts according to Examples 1, 2 and 4, a peak (iX 3 ) having a diffraction angle 2θ of 53.0 ° to 54.0 ° was observed. Further, for the catalysts according to Examples 1 and 2, a peak (iY 4 ) having a diffraction angle 2θ of 61.0 ° to 62.0 ° was observed. In addition, some of the catalysts according to Examples 1 to 4 had a small peak (iY 2 or simply iY) having a diffraction angle 2θ of 39.0 ° to 40.0 °.
On the other hand, with respect to the catalysts according to Comparative Examples 2 and 4, a peak (iX 1 ) having a diffraction angle 2θ of 25.0 ° to 27.0 ° and a peak (iX 2) having a diffraction angle of 37.0 ° to 38.0 ° (iX 2 or simply iX). ) Was observed. Further, with respect to the catalyst according to Comparative Example 4, a peak (iX 3 ) having a diffraction 2θ of 53.0 ° to 54.0 ° was observed, and a peak (iY 2 ) having a diffraction angle 2θ of 39.0 ° to 40.0 ° was observed. Or simply iY) was not observed. Further, regarding the catalyst according to Comparative Example 2, a peak having a diffraction angle 2θ of 34.0 ° to 35.0 ° (iY 1 ) and a peak having a diffraction angle 2θ of 39.0 ° to 40.0 ° (iY 2 or simply). iY), a peak with a diffraction angle of 2θ of 52.0 ° to 52.9 ° (iY 3 ), and a peak with a diffraction angle of 2θ of 61.0 ° to 62.0 ° (iY 4 ) were observed. Here, regarding the catalyst according to Comparative Example 2, iX 2 is observed, but the intensity of iY 2 is large, and iY 1 to iY 4 are observed, so that molybdenum carbide (Mo 2 C) is dominant. Conceivable.
また、実施例１〜実施例４に係る触媒のピーク強度比（表１の「３９．０°〜４０．０°（ｉＹ）／３７．０°〜３８．０°（ｉＸ）」）は、比較例に係る触媒のそれ（３．６８）より低かった。すなわち、高い触媒活性を示す実施例１〜実施例４に係る触媒は、ピーク強度比が０．５４〜０．９８を示す構造を有する点で特徴づけられた。 Further, the peak intensity ratio of the catalyst according to Examples 1 to 4 (“39.0 ° to 40.0 ° (iY) /37.0 ° to 38.0 ° (iX)” in Table 1) is determined. It was lower than that of the catalyst according to the comparative example (3.68). That is, the catalysts according to Examples 1 to 4 showing high catalytic activity were characterized in that they had a structure showing a peak intensity ratio of 0.54 to 0.98.
［電気化学測定：酸素還元反応活性評価］
次に、電気化学測定により、酸素還元反応活性を評価した。まず、触媒スラリーを調製した。すなわち、上述の実施例１〜４及び比較例１〜４それぞれにおいて、触媒５ｍｇと、５重量％Ｎａｆｉｏｎ（登録商標）溶液（Ａｌｄｒｉｃｈ社製）５０μＬと、エタノール１５０μＬと、蒸留水１５０μＬとを混合し、２０分間、超音波処理することにより、触媒が均一に分散された触媒スラリーを調製した。
[Electrochemical measurement: Evaluation of oxygen reduction reaction activity]
Next, the oxygen reduction reaction activity was evaluated by electrochemical measurement. First, a catalyst slurry was prepared. That is, in each of Examples 1 to 4 and Comparative Examples 1 to 4 described above, 5 mg of the catalyst, 50 μL of a 5 wt% Nafion (registered trademark) solution (manufactured by Aldrich), 150 μL of ethanol, and 150 μL of distilled water were mixed. , The catalyst slurry in which the catalyst was uniformly dispersed was prepared by sonication for 20 minutes.
次に、この触媒スラリー１．７８μＬをピペットで吸い取り、回転リングディスク電極装置（ＲＲＤＥ−３Ａ、株式会社 ＢＡＳ製）のリングディスク電極（直径４ｍｍ）に塗布し、乾燥させることにより、作用電極を作製した。また、可逆水素電極を参照電極として用い、ガラス状炭素を対極として用いた。電解液としては、０．５ｍｏｌ／ＬＨ２ＳＯ４水溶液を用いた。 Next, 1.78 μL of this catalyst slurry is sucked up with a pipette, applied to a ring disk electrode (diameter 4 mm) of a rotating ring disk electrode device (RRDE-3A, manufactured by BAS Co., Ltd.), and dried to prepare a working electrode. did. A reversible hydrogen electrode was used as a reference electrode, and glassy carbon was used as a counter electrode. As the electrolytic solution, a 0.5 mol / LH 2 SO 4 aqueous solution was used.
そして、実施例１〜４及び比較例１〜４の触媒を三極式の作用電極に用いてサイクリックボルタンメトリー及び酸素還元反応に関するリニアスイープボルタンメトリーを実施した。 Then, cyclic voltammetry and linear sweep voltammetry related to the oxygen reduction reaction were carried out using the catalysts of Examples 1 to 4 and Comparative Examples 1 to 4 as a tripolar working electrode.
サイクリックボルタンメトリーにおいては、まず、２５℃で窒素を３０分間バブリングすることにより電解液を窒素飽和させた後に、測定を開始した。すなわち、この窒素飽和させた電解液を用い、電極を回転させることなく、２５℃にて、走査速度５０ｍＶ／秒で、１．０Ｖ（ｖｓ．ＲＨＥ）から０Ｖ（ｖｓ．ＲＨＥ）まで電位を掃引するサイクルを実施し、作用電極に流れる電流値を測定した。 In cyclic voltammetry, first, the electrolytic solution was saturated with nitrogen by bubbling nitrogen at 25 ° C. for 30 minutes, and then the measurement was started. That is, using this nitrogen-saturated electrolytic solution, the potential is swept from 1.0 V (vs. RHE) to 0 V (vs. RHE) at 25 ° C. and a scanning speed of 50 mV / sec without rotating the electrode. The current value flowing through the working electrode was measured.
酸素還元反応に関するリニアスイープボルタンメトリーにおいては、まず、２５℃で酸素を２０分間バブリングすることにより電解液を酸素飽和させた後、自然電位を測定した。
次いで、初期電位１．０Ｖ（ｖｓ．ＲＨＥ）を６００秒印加した後に、酸素飽和させた電解液を用い、電極を回転速度１５００ｒｐｍで回転させ、２５℃にて、走査速度１ｍＶ／秒にて、１．０Ｖ（ｖｓ．ＲＨＥ）から０Ｖ（ｖｓ．ＲＨＥ）まで電位を掃引し、作用電極に流れる電流値を測定した。
In the linear sweep voltammetry related to the oxygen reduction reaction, first, the electrolytic solution was oxygen-saturated by bubbling oxygen at 25 ° C. for 20 minutes, and then the natural potential was measured.
Next, after applying an initial potential of 1.0 V (vs. RHE) for 600 seconds, the electrode was rotated at a rotation speed of 1500 rpm using an oxygen-saturated electrolytic solution, and at 25 ° C. and a scanning speed of 1 mV / sec. The potential was swept from 1.0 V (vs. RHE) to 0 V (vs. RHE), and the current value flowing through the working electrode was measured.
図９に、サイクリックボルタンメトリーにおいて得られたボルタモグラムの一例を示す。図９において、横軸は印加された電位（Ｖｖｓ．ＲＨＥ）を示し、縦軸は電流密度（ｍＡ／ｃｍ２）を示す。図９は、実施例１〜４及び比較例１、２の触媒を作用電極に用いた場合の結果を示す。 FIG. 9 shows an example of a voltamogram obtained by cyclic voltammetry. In FIG. 9, the horizontal axis represents the applied potential (Vvs. RHE) and the vertical axis represents the current density (mA / cm 2 ). FIG. 9 shows the results when the catalysts of Examples 1 to 4 and Comparative Examples 1 and 2 were used as the working electrode.
図９に示すように、実施例１、２、４において、１．０Ｖ（ｖｓ．ＲＨＥ）以下、０．９Ｖ（ｖｓ．ＲＨＥ）以上の間で酸化モリブデン由来の酸化反応を示すピーク（ｃｄＡ）が、実施例２には、０．９Ｖ（ｖｓ．ＲＨＥ）未満、０．７Ｖ（ｖｓ．ＲＨＥ）以上の間で炭化モリブデン由来の酸化反応を示すピーク（ｃｄＢ）が現れた。また、いずれの触媒にも、０〜０．６５Ｖの間にリンモリブデン酸由来のＲｅｄｏｘピークが表れた。 As shown in FIG. 9, in Examples 1, 2 and 4, a peak (cdA) showing an oxidation reaction derived from molybdenum oxide between 1.0 V (vs. RHE) or less and 0.9 V (vs. RHE) or more. However, in Example 2, a peak (cdB) showing an oxidation reaction derived from molybdenum carbide appeared between 0.9 V (vs. RHE) and 0.7 V (vs. RHE) or more. In addition, a redox peak derived from phosphomolybdic acid appeared between 0 and 0.65 V in each catalyst.
これに対し、図９に示すように、比較例１の触媒を作用電極に用いた場合には、リンモリブデン酸由来のＲｅｄｏｘピークが表れ、酸化モリブデン由来と炭化モリブデン由来の酸化反応を示すピークは現れなかった。また、比較例２の触媒を作用電極に用いた場合には、リンモリブデン酸由来のＲｅｄｏｘピークと炭化モリブデン由来の酸化反応を示すピークが現れ、酸化モリブデン由来のピークは現れなかった。 On the other hand, as shown in FIG. 9, when the catalyst of Comparative Example 1 was used as the working electrode, the Redox peak derived from phosphomolybdic acid appeared, and the peak showing the oxidation reaction derived from molybdenum oxide and molybdenum carbide was observed. Did not appear. Further, when the catalyst of Comparative Example 2 was used as the working electrode, a redox peak derived from phosphomolybdic acid and a peak showing an oxidation reaction derived from molybdenum carbide appeared, and a peak derived from molybdenum oxide did not appear.
また、図９に示される電流密度ピークの比に着目すると、実施例１〜実施例４に係る触媒の電流密度ピークの比（ｃｄＢ／ｃｄＡ）は、比較例に係る触媒のそれ（９．７）より低かった。すなわち、高い触媒活性を示す実施例１〜実施例４に係る触媒は、電流密度のピーク比（ｃｄＢ／ｃｄＡ）が０．１〜１．２を示す組成を有する点で特徴づけられた。 Focusing on the ratio of the current density peaks shown in FIG. 9, the ratio of the current density peaks of the catalysts according to Examples 1 to 4 (cdB / cdA) is that of the catalyst according to the comparative example (9.7). ) Was lower. That is, the catalysts according to Examples 1 to 4 showing high catalytic activity were characterized in that they had a composition showing a peak ratio (cdB / cdA) of current density of 0.1 to 1.2.
図１０に、酸素還元反応に関するリニアスイープボルタンメトリーにおいて得られたボルタモグラムの一例を示す。図１０において、横軸は印加された電位（Ｖｖｓ．ＲＨＥ）を示し、縦軸は電流密度（ｍＡ／ｃｍ２）を示す。図１０は、実施例１〜４の触媒を作用電極に用いた場合と、比較例１の触媒を作用電極に用いた場合の結果を示す。 FIG. 10 shows an example of a voltamogram obtained by linear sweep voltammetry related to the oxygen reduction reaction. In FIG. 10, the horizontal axis represents the applied potential (Vvs. RHE) and the vertical axis represents the current density (mA / cm 2 ). FIG. 10 shows the results when the catalysts of Examples 1 to 4 were used for the working electrode and when the catalyst of Comparative Example 1 was used for the working electrode.
表１と図１０より、実施例１〜４の触媒を作用電極に用いた場合では、比較例１〜４の触媒を作用電極に用いた場合よりも酸素還元活性の開始電位が高く、より高い還元電流が得られたことが分かる。 From Table 1 and FIG. 10, when the catalysts of Examples 1 to 4 were used for the working electrode, the starting potential of the oxygen reduction activity was higher and higher than that when the catalysts of Comparative Examples 1 to 4 were used for the working electrode. It can be seen that the reduction current was obtained.
［電気化学測定：過酸化水素還元反応活性評価］
さらに、電気化学測定により、過酸化水素還元反応活性を評価した。まず、触媒スラリーを調製した。すなわち、上述の実施例１〜４及び比較例１〜３それぞれにおいて、触媒５ｍｇと、５重量％Ｎａｆｉｏｎ（登録商標）溶液（Ａｌｄｒｉｃｈ社製）５０μＬと、エタノール１５０μＬと、蒸留水１５０μＬとを混合し、２０分間、超音波処理することにより、触媒が均一に分散された触媒スラリーを調製した。
[Electrochemical measurement: Evaluation of hydrogen peroxide reduction reaction activity]
Furthermore, the hydrogen peroxide reduction reaction activity was evaluated by electrochemical measurement. First, a catalyst slurry was prepared. That is, in each of Examples 1 to 4 and Comparative Examples 1 to 3 described above, 5 mg of the catalyst, 50 μL of a 5 wt% Nafion (registered trademark) solution (manufactured by Aldrich), 150 μL of ethanol, and 150 μL of distilled water were mixed. , The catalyst slurry in which the catalyst was uniformly dispersed was prepared by sonication for 20 minutes.
次に、この触媒スラリー１．７８μＬをピペットで吸い取り、回転リングディスク電極装置（ＲＲＤＥ−３Ａ、株式会社 ＢＡＳ製）のリングディスク電極（直径４ｍｍ）に塗布し、乾燥させることにより、作用電極を作製した。また、可逆水素電極を参照電極として用い、ガラス状炭素を対極として用いた。電解液としては、０．５ｍｏｌ／ＬＨ２ＳＯ４水溶液を溶媒にして１ｍＭとなるように過酸化水素（Ｈ２Ｏ２）を加えた溶液を用いた。 Next, 1.78 μL of this catalyst slurry is sucked up with a pipette, applied to a ring disk electrode (diameter 4 mm) of a rotating ring disk electrode device (RRDE-3A, manufactured by BAS Co., Ltd.), and dried to prepare a working electrode. did. A reversible hydrogen electrode was used as a reference electrode, and glassy carbon was used as a counter electrode. As the electrolytic solution, a solution was used in which a 0.5 mol / LH 2 SO 4 aqueous solution was used as a solvent and hydrogen peroxide (H 2 O 2 ) was added so as to be 1 mM.
そして、実施例１〜４及び比較例１〜３の触媒を三極式の作用電極に用いて過酸化水素還元反応に関するリニアスイープボルタンメトリーを実施した。 Then, linear sweep voltammetry related to the hydrogen peroxide reduction reaction was carried out using the catalysts of Examples 1 to 4 and Comparative Examples 1 to 3 as a tripolar working electrode.
まず、２５℃で窒素を３０分間バブリングすることにより電解液を窒素飽和させ、溶存酸素を除いた後、自然電位を測定した。
次いで、初期電位１．０Ｖ（ｖｓ．ＲＨＥ）を６００秒印加した後に、窒素飽和させ、溶存酸素を取り除いた電解液を用い、電極を回転速度１５００ｒｐｍで回転させ、２５℃にて、走査速度１ｍＶ／秒にて、１．０（ｖｓ．ＲＨＥ）から０Ｖ（ｖｓ．ＲＨＥ）まで電位を掃引し、作用電極に流れる電流値を測定した。
First, the electrolytic solution was saturated with nitrogen by bubbling nitrogen at 25 ° C. for 30 minutes to remove dissolved oxygen, and then the natural potential was measured.
Next, after applying an initial potential of 1.0 V (vs. RHE) for 600 seconds, the electrode was rotated at a rotation speed of 1500 rpm using an electrolytic solution that was saturated with nitrogen and the dissolved oxygen was removed, and the scanning speed was 1 mV at 25 ° C. At / sec, the potential was swept from 1.0 (vs. RHE) to 0 V (vs. RHE), and the value of the current flowing through the working electrode was measured.
図１１に、過酸化水素還元反応に関するリニアスイープボルタンメトリーにおいて得られたボルタモグラムの一例を示す。図１１において、横軸は印加された電位（Ｖｖｓ．ＲＨＥ）を示し、縦軸は電流密度（ｍＡ／ｃｍ２）を示す。図１１は、実施例１及び比較例１の触媒を作用電極に用いた場合の結果を示す。 FIG. 11 shows an example of a voltamogram obtained by linear sweep voltammetry related to the hydrogen peroxide reduction reaction. In FIG. 11, the horizontal axis represents the applied potential (Vvs. RHE) and the vertical axis represents the current density (mA / cm 2 ). FIG. 11 shows the results when the catalysts of Example 1 and Comparative Example 1 were used as the working electrode.
表１と図１１より、実施例１〜４の触媒を作用電極に用いた場合では、比較例１〜３の触媒を作用電極に用いた場合よりも過酸化水素還元に対する０．１Ｖの時の電流密度の絶対値が大きく、過酸化水素還元電流が増加していることが分かる。
From Table 1 and FIG. 11, when the catalysts of Examples 1 to 4 were used for the working electrode, the voltage was 0.1 V for hydrogen peroxide reduction as compared with the case where the catalysts of Comparative Examples 1 to 3 were used for the working electrode. It can be seen that the absolute value of the current density is large and the hydrogen peroxide reduction current is increasing.
Claims (9)
前記ヘテロポリ酸及び／または前記ヘテロポリ酸塩の金属酸素酸骨格中に金属原子としてモリブデン、または、モリブデン及びバナジウムを有し、
前記金属酸化物の金属原子としてモリブデン、または、モリブデン及びバナジウムを有し、
前記金属酸化物として酸化モリブデン、または、酸化モリブデン及び酸化バナジウムを含み、
かつ、サイクリックボルタンメトリーにおいて、電極電位を１．０Ｖ（ｖｓ．ＲＨＥ）から０Ｖ（ｖｓ．ＲＨＥ）まで掃引した場合に、１サイクル目における、１．０Ｖ（ｖｓ．ＲＨＥ）以下、０．９Ｖ（ｖｓ．ＲＨＥ）以上の間で生じる電流密度のピーク（ｃｄＡ）と、０．９Ｖ（ｖｓ．ＲＨＥ）未満、０．７Ｖ（ｖｓ．ＲＨＥ）以上の間で生じる電流密度のピーク（ｃｄＢ）との比（ｃｄＢ／ｃｄＡ）が０超、２未満であること、
を特徴とする触媒（ただし、コバルト、鉄、ニッケル、クロム、マンガンから選ばれる１種以上の金属元素を中心金属とするポルフィリン錯体を有しない。）。 A catalyst for a fuel cell cathode side electrode containing a heteropolyacid and / or a heteropolylate, a metal oxide, and a conductive material.
Molybdenum, or molybdenum and vanadium, as metal atoms in the metal oxygen skeleton of the heteropolyacid and / or the heteropolyate.
It has molybdenum or molybdenum and vanadium as metal atoms of the metal oxide.
The metal oxide contains molybdenum oxide or molybdenum oxide and vanadium oxide.
Moreover, in cyclic voltammetry, when the electrode potential is swept from 1.0 V (vs. RHE) to 0 V (vs. RHE), 1.0 V (vs. RHE) or less in the first cycle, 0.9 V ( The current density peak (cdA) occurring between vs. RHE) and above and the current density peak (cdB) occurring between 0.7V (vs.RHE) and above below 0.9V (vs.RHE). The ratio (cdB / cdA) is greater than 0 and less than 2.
(However, it does not have a porphyrin complex having one or more metal elements selected from cobalt, iron, nickel, chromium, and manganese as a central metal).
粉末Ｘ線回折法における、回折角２θ＝３７．０°以上、３８．０°以下の範囲内のピーク強度（ｉＸ）と、回折角２θ＝３９．０°以上、４０．０°以下の範囲内のピーク強度（ｉＹ）との比（ｉＹ／ｉＸ）が０超、３．６未満であること、
を特徴とする請求項１ないし４の何れかに記載の触媒。 A catalyst for a fuel cell cathode side electrode containing a heteropolyacid and / or a heteropolylate, a metal oxide, and a conductive material.
Peak intensity (iX) in the range of diffraction angle 2θ = 37.0 ° or more and 38.0 ° or less in the powder X-ray diffraction method, and the range of diffraction angle 2θ = 39.0 ° or more and 40.0 ° or less. The ratio (iY / iX) to the peak intensity (iY) is more than 0 and less than 3.6.
The catalyst according to any one of claims 1 to 4.
前記ヘテロポリ酸及び／またはヘテロポリ酸塩は、ケギン型構造を有すること、
を特徴とする請求項１ないし５の何れかに記載の触媒。 A catalyst for a fuel cell cathode side electrode containing a heteropolyacid and / or a heteropolylate, a metal oxide, and a conductive material.
The heteropolyacid and / or heteropolylate has a kegin-type structure.
The catalyst according to any one of claims 1 to 5.
金属酸素酸骨格中に金属原子としてモリブデン及び／またはバナジウムを有するヘテロポリ酸及び／またはヘテロポリ酸塩と、炭素系の導電性材料とを混合し、ヘテロポリ酸及び／またはヘテロポリ酸塩を４〜４９重量％、及び炭素系の導電性材料を５１〜９６重量％含む混合物を得る第一の工程、
および前記混合物を５００℃から９００℃で熱処理する第二の工程、
を有することを特徴とする触媒の製造方法（ただし、前記第一の工程において、コバルト、鉄、ニッケル、クロム、マンガンから選ばれる１種以上の金属元素を中心金属とするポルフィリン錯体を混合しない。）。 A method for producing a catalyst for a fuel cell cathode side electrode, which comprises a heteropolyacid and / or a heteropolylate, a metal oxide, and a conductive material.
Heteropolyacids and / or heteropolylates having molybdenum and / or vanadium as metal atoms in the metal oxygen acid skeleton are mixed with a carbon-based conductive material to add 4-49 weight of heteropolyacid and / or heteropolylate. %, And the first step of obtaining a mixture containing 51-96% by weight of the carbon-based conductive material,
And a second step of heat treating the mixture at 500 ° C to 900 ° C,
(However, in the first step, a porphyrin complex having one or more metal elements selected from cobalt, iron, nickel, chromium, and manganese as a central metal is not mixed. ).
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