JP5579256B2 - メタンの電気化学的酸化のための触媒及び方法 - Google Patents
メタンの電気化学的酸化のための触媒及び方法 Download PDFInfo
- Publication number
- JP5579256B2 JP5579256B2 JP2012507793A JP2012507793A JP5579256B2 JP 5579256 B2 JP5579256 B2 JP 5579256B2 JP 2012507793 A JP2012507793 A JP 2012507793A JP 2012507793 A JP2012507793 A JP 2012507793A JP 5579256 B2 JP5579256 B2 JP 5579256B2
- Authority
- JP
- Japan
- Prior art keywords
- catalyst
- precursor
- platinum
- heteropolyanion
- methane
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims description 98
- 239000003054 catalyst Substances 0.000 title claims description 69
- 238000000034 method Methods 0.000 title claims description 22
- 238000006056 electrooxidation reaction Methods 0.000 title 1
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 72
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 54
- 239000002243 precursor Substances 0.000 claims description 41
- 229910021645 metal ion Inorganic materials 0.000 claims description 40
- 238000007254 oxidation reaction Methods 0.000 claims description 36
- 230000003647 oxidation Effects 0.000 claims description 35
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 30
- 229910052697 platinum Inorganic materials 0.000 claims description 26
- 239000000446 fuel Substances 0.000 claims description 24
- 238000006243 chemical reaction Methods 0.000 claims description 22
- 239000002904 solvent Substances 0.000 claims description 22
- 239000000203 mixture Substances 0.000 claims description 21
- ROFVEXUMMXZLPA-UHFFFAOYSA-N Bipyridyl Chemical compound N1=CC=CC=C1C1=CC=CC=N1 ROFVEXUMMXZLPA-UHFFFAOYSA-N 0.000 claims description 15
- 239000000463 material Substances 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 13
- 229910021397 glassy carbon Inorganic materials 0.000 claims description 12
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 11
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 11
- HRGDZIGMBDGFTC-UHFFFAOYSA-N platinum(2+) Chemical compound [Pt+2] HRGDZIGMBDGFTC-UHFFFAOYSA-N 0.000 claims description 10
- 239000010936 titanium Substances 0.000 claims description 10
- 229910052719 titanium Inorganic materials 0.000 claims description 10
- 229910052751 metal Inorganic materials 0.000 claims description 9
- 239000002184 metal Substances 0.000 claims description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 7
- 229910052799 carbon Inorganic materials 0.000 claims description 7
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 6
- 239000003446 ligand Substances 0.000 claims description 6
- 238000001704 evaporation Methods 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 5
- CLSUSRZJUQMOHH-UHFFFAOYSA-L platinum dichloride Chemical group Cl[Pt]Cl CLSUSRZJUQMOHH-UHFFFAOYSA-L 0.000 claims description 5
- 239000004020 conductor Substances 0.000 claims description 4
- 239000002245 particle Substances 0.000 claims description 4
- FOSZYDNAURUMOT-UHFFFAOYSA-J azane;platinum(4+);tetrachloride Chemical compound N.N.N.N.[Cl-].[Cl-].[Cl-].[Cl-].[Pt+4] FOSZYDNAURUMOT-UHFFFAOYSA-J 0.000 claims description 3
- 238000000151 deposition Methods 0.000 claims description 3
- 239000004744 fabric Substances 0.000 claims description 3
- 230000008569 process Effects 0.000 claims description 3
- 238000005507 spraying Methods 0.000 claims description 3
- 150000001298 alcohols Chemical class 0.000 claims description 2
- 150000003058 platinum compounds Chemical class 0.000 claims description 2
- 239000013110 organic ligand Substances 0.000 claims 1
- 150000002500 ions Chemical class 0.000 description 18
- 239000000243 solution Substances 0.000 description 17
- 239000001257 hydrogen Substances 0.000 description 7
- 229910052739 hydrogen Inorganic materials 0.000 description 7
- -1 C 4 alcohols Chemical class 0.000 description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 5
- 230000009467 reduction Effects 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 239000007853 buffer solution Substances 0.000 description 2
- 238000000855 fermentation Methods 0.000 description 2
- 230000004151 fermentation Effects 0.000 description 2
- 125000005842 heteroatom Chemical group 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 229920000447 polyanionic polymer Polymers 0.000 description 2
- 238000010248 power generation Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 101710134784 Agnoprotein Proteins 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- 238000012443 analytical study Methods 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 229940045985 antineoplastic platinum compound Drugs 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229940075397 calomel Drugs 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 150000001869 cobalt compounds Chemical class 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical compound Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000002848 electrochemical method Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 1
- 239000005431 greenhouse gas Substances 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 229910052754 neon Inorganic materials 0.000 description 1
- GKAOGPIIYCISHV-UHFFFAOYSA-N neon atom Chemical compound [Ne] GKAOGPIIYCISHV-UHFFFAOYSA-N 0.000 description 1
- 150000002826 nitrites Chemical class 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229910017464 nitrogen compound Inorganic materials 0.000 description 1
- 150000002830 nitrogen compounds Chemical class 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 230000037361 pathway Effects 0.000 description 1
- 239000010908 plant waste Substances 0.000 description 1
- XTUSEBKMEQERQV-UHFFFAOYSA-N propan-2-ol;hydrate Chemical compound O.CC(C)O XTUSEBKMEQERQV-UHFFFAOYSA-N 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
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
- H01M4/92—Metals of platinum group
-
- 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
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/56—Platinum group metals
- B01J23/64—Platinum group metals with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/652—Chromium, molybdenum or tungsten
- B01J23/6527—Tungsten
-
- 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
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
- B01J23/8933—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/8993—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with chromium, molybdenum or tungsten
-
- 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
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J27/188—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum, tungsten or polonium
-
- 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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
- B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
- B01J31/181—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine
- B01J31/1815—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine with more than one complexing nitrogen atom, e.g. bipyridyl, 2-aminopyridine
-
- 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
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0215—Coating
- B01J37/0219—Coating the coating containing organic compounds
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/50—Carbon dioxide
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/48—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by oxidation reactions with formation of hydroxy groups
-
- 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
- H01M4/8647—Inert electrodes with catalytic activity, e.g. for fuel cells consisting of more than one material, e.g. consisting of composites
- H01M4/8652—Inert electrodes with catalytic activity, e.g. for fuel cells consisting of more than one material, e.g. consisting of composites as mixture
-
- 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
- H01M4/8647—Inert electrodes with catalytic activity, e.g. for fuel cells consisting of more than one material, e.g. consisting of composites
- H01M4/8657—Inert electrodes with catalytic activity, e.g. for fuel cells consisting of more than one material, e.g. consisting of composites layered
-
- 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
- H01M4/8803—Supports for the deposition of the catalytic active composition
- H01M4/8807—Gas diffusion layers
-
- 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
- H01M4/8825—Methods for deposition of the catalytic active composition
- H01M4/8828—Coating with slurry or ink
-
- 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
- H01M4/8825—Methods for deposition of the catalytic active composition
- H01M4/8842—Coating using a catalyst salt precursor in solution followed by evaporation and reduction of the precursor
-
- 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
- H01M4/8825—Methods for deposition of the catalytic active composition
- H01M4/886—Powder spraying, e.g. wet or dry powder spraying, plasma spraying
-
- 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
- H01M4/90—Selection of catalytic material
- H01M4/9008—Organic or organo-metallic compounds
-
- 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
- H01M4/92—Metals of platinum group
- H01M4/923—Compounds thereof with non-metallic elements
-
- 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
- H01M8/08—Fuel cells with aqueous electrolytes
-
- 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
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/66—Silver or gold
- B01J23/68—Silver or gold with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/683—Silver or gold with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum or tungsten
- B01J23/687—Silver or gold with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum or tungsten with tungsten
-
- 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
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/82—Metals of the platinum group
- B01J2531/828—Platinum
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2250/00—Fuel cells for particular applications; Specific features of fuel cell system
- H01M2250/20—Fuel cells in motive systems, e.g. vehicle, ship, plane
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2250/00—Fuel cells for particular applications; Specific features of fuel cell system
- H01M2250/30—Fuel cells in portable systems, e.g. mobile phone, laptop
-
- 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
- Y02B—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO BUILDINGS, e.g. HOUSING, HOUSE APPLIANCES OR RELATED END-USER APPLICATIONS
- Y02B90/00—Enabling technologies or technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02B90/10—Applications of fuel cells in buildings
-
- 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
-
- 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
- Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
- Y02T90/00—Enabling technologies or technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02T90/40—Application of hydrogen technology to transportation, e.g. using fuel cells
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Inorganic Chemistry (AREA)
- Composite Materials (AREA)
- Life Sciences & Earth Sciences (AREA)
- Sustainable Development (AREA)
- Sustainable Energy (AREA)
- Catalysts (AREA)
- Inert Electrodes (AREA)
- Electrodes For Compound Or Non-Metal Manufacture (AREA)
- Carbon And Carbon Compounds (AREA)
Description
(a)直鎖若しくは分岐状のC1〜C4アルコール、直鎖若しくは分岐状のC1〜C4アルコールの混合物、又は水と少なくとも1つの直鎖若しくは分岐状のC1〜C4アルコールとの混合物から選択される溶媒中に、H4SiW12O40及びK6P2W18O62から選択されるヘテロポリアニオンHPAを溶解させる工程、
(b)電子を伝導する材料で作られる支持体の少なくとも1つの表面上に工程(a)で得られる溶液を堆積させる工程、
(c)工程(b)で堆積させた溶液から溶媒を蒸発させる工程、
(d)工程(c)で得られるヘテロポリアニオンで覆った表面全体に、水、水と少なくとも1つの直鎖又は分岐状のC1〜C4アルコールとの混合物、及び直鎖又は分岐状のC1〜C4アルコールの混合物から選択される溶媒中に、有機リガンド又は無機リガンドによって必要に応じて錯体形成される酸化状態IIの白金前駆物質、並びにAg+、Ru2+、Co2+、Ni2+、Fe2+及びこれらの2つ以上の混合物から選択される金属イオン(複数可)Mの前駆物質を含む溶液を噴霧する工程、
(e)工程(d)で噴霧した溶液から溶媒を蒸発させる工程
を含むことを特徴とする、方法を提供する。
実施例1:
メタンの酸化の分析研究のための電極の調製
1mL当たり10mgの濃度のイソプロパノール中のケギンヘテロポリアニオン(H4SiW12O40)の溶液、又は1mL当たり5mgの濃度の水/イソプロパノール中のドーソンヘテロポリアニオン(K6P2W18O62)の溶液2μLを、直径3ミリメートルのグラッシーカーボンの研磨した表面上に堆積させる。イソプロパノール溶媒の蒸発後、2×10−5Mの濃度の酸化状態IIの白金イオンの前駆物質(この場合、PtCl2、Pt(Bipy)Cl2又はPt(NH3)4Cl2)及び0.08Mの濃度のAgNO3の形態の金属イオンAg+の前駆物質を含む混合物2μLを堆積させる。使用する溶媒は、水又は水/イソプロパノール混合物である。続いて、この溶媒を蒸発させる。ネオン電球の下で、H4SiW12O40を用いた場合には、このフィルムが薄い場合、複数色に呈色した輪(areola)が見られ、又はK6P2W18O62を用いた場合は、オフホワイト色の輪が見られる。
実施例2:
メタンのCO2への直接変換に関する実施例1で得られる電極の試験
実施例1で得られる電極を、Na2SO4/H2SO4の緩衝溶液(pH3)へ浸して、電流が安定化するまでアルゴン下で飽和カロメル電極(SCE)に関して0.9ボルト〜1.7ボルトで循環させる。およそ30分〜1時間かかる。次に、溶液を、表面でのメタンの拡散によって飽和させる。飽和は緩やかに進む。触媒作用は、3時間超持続し得る。
実施例3:
本発明による触媒を用いた高表面積の電極の調製
1mL当たり10mgの濃度のイソプロパノール中のケギンヘテロポリアニオン(H4SiW12O40)の溶液、又は1mL当たり5mgの濃度の水/イソプロパノール中のドーソンヘテロポリアニオン(K6P2W18O62)の溶液を、3cm2の研磨グラッシーカーボン表面全体に噴霧する。
実施例4:
メタンのCO2への直接変換に関する実施例3の電極の試験
実施例3で得られる電極を、0.1M Na2SO4の緩衝溶液(pH3)で満たした2区画セルの区画中に浸す。セルの他の区画は、バルク白金で作られる電極を含む。メタンの触媒との接触により、バルク白金電極(陽極)と本発明による電極(陰極)との間の電位差が、0.4ボルトまで増加し、これにより、CH4の触媒への固定が明らかに示される。
実施例5:メタン燃料電池用の電極の調製
1mL当たり10mgの濃度のイソプロパノール中のケギンヘテロポリアニオン(H4SiW12O40)の溶液、又は1mL当たり5mgの濃度の水/イソプロパノール中のドーソンヘテロポリアニオン(K6P2W18O62)の溶液1mLを、25cm2のチタンスポンジ全体に噴射する。イソプロパノールを蒸発させる。次に、イソプロパノール0.3mL中の前駆物質PtCl2、Pt(Bipy)Cl2又はPt(NH3)4Cl2の形態で添加される10−4Mの濃度の酸化状態IIの白金イオンを含む溶液0.1mLと、10−1Mの濃度の金属イオンAg+とを含む溶液0.1mLを含む溶液を、ヘテロポリアニオンで覆われたチタンフォームの表面上に堆積させる。
Claims (22)
- ヘテロポリアニオンHPAの粒子上に支持される白金(II)前駆物質を含むことを特徴とする触媒であって、
前記ヘテロポリアニオンHPAが、H4SiW12O40及びK6P2W18O62か
ら選択される、メタンのメタノールへの変換のための、又は、メタンのCO 2 への変換のための触媒。 - 前記白金(II)前駆物質が、有機リガンド又は無機リガンドによって錯体形成される酸化状態IIの白金前駆物質であることを特徴とする、請求項1に記載の触媒。
- 前記白金(II)前駆物質が、式PtCl2の塩化白金、下記式:
- 前記白金(II)前駆物質が、(Bipy)PtCl2又はPt(NH3)4Cl2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触媒。
- 前記ヘテロポリアニオンHPAが、K6P2W18O62であ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触媒。
- Ag + 、Ru 2+ 、Ni 2+ 、Co 2+ 、Fe 2+ 及びこれらの2つ以上の混合物から選択される金属イオン(複数可)Mの前駆物質を含まないことを特徴とする、請求項1〜5のいずれか1項に記載の触媒。
- Ag + 、Ru 2+ 、Ni 2+ 、Co 2+ 、Fe 2+ 及びこれらの2つ以上の混合物から選択される金属イオン(複数可)Mの前駆物質をさらに含むことを特徴とし、メタンのCO 2 への変換のために用いられる、請求項1〜5のいずれか1項に記載の触媒。
- 金属イオン(複数可)の前記前駆物質が、Ag + 前駆物質であることを特徴とする、請求項7に記載の触媒。
- その少なくとも1つの表面上に請求項1〜5、7又は8に記載の触媒が堆積している、電子を伝導する材料で作られる支持体を含むことを特徴とする電極。
- 燃料電池の電極である、請求項9に記載の電極。
- 前記電子を伝導する前記材料が、バルクグラッシーカーボン、グラッシーカーボンファ
ブリック、グラッシーカーボンフェルト、又はチタン金属のスポンジから選択されること
を特徴とする、請求項9又は10に記載の電極。 - 請求項9〜11のいずれか1項に記載の電極の製造方法であって、
(a)直鎖若しくは分岐状のC1〜C4アルコール、直鎖若しくは分岐状のC1〜C4アルコールの混合物、又は水と少なくとも1つの直鎖若しくは分岐状のC1〜C4アルコールとの混合物から選択される溶媒中に、H4SiW12O40及びK6P2W18O62から選択されるヘテロポリアニオンHPAを溶解させる工程、
(b)電子を伝導する材料で作られる支持体の少なくとも1つの表面上に工程(a)で得られる前記溶液を堆積させる工程、
(c)工程(b)で堆積させた前記溶液から前記溶媒を蒸発させる工程、
(d)工程(c)で得られるヘテロポリアニオンでコーティングした前記表面全体に、水、水と少なくとも1つの直鎖又は分岐状のC1〜C4アルコールとの混合物、直鎖又は分岐状のC1〜C4アルコール、及び直鎖又は分岐状のC1〜C4アルコールの混合物から選択される溶媒中に、有機リガンド又は無機リガンドによって必要に応じて錯体形成される酸化状態IIの白金前駆物質、並びにAg+、Ru2+、Co2+、Ni2+、Fe2+及びこれらの2つ以上の混合物から選択される金属イオン(複数可)Mの前駆物質を含む溶液を噴霧する工程、並びに
(e)工程(d)で噴霧した前記溶液から前記溶媒を蒸発させる工程を含むことを特徴とする、方法。 - 工程(a)及び工程(c)における前記溶媒が、イソプロパノールであることを特徴とする、請求項12に記載の方法。
- 電子を伝導する前記材料が、バルクグラッシーカーボン、カーボンフェルト、カーボンファブリック、及びチタン金属のスポンジから選択されることを特徴とする、請求項12又は13に記載の方法。
- 酸化状態IIの前記白金前駆物質が、PtCl2、(Bipy)PtCl2及びPt(NH3)4Cl2から選択されることを特徴とする、請求項12〜14のいずれか一項に記載の方法。
- 酸化状態IIの前記白金化合物が、(Bipy)PtCl2及びPt(NH3)4Cl2から選択されることを特徴とする、請求項12〜15のいずれか一項に記載の方法。
- 金属イオン(複数可)の前記前駆物質の前記金属イオン(複数可)MがAg+であることを特徴とする、請求項12〜16のいずれか一項に記載の方法。
- 前記ヘテロポリアニオンが、K6P2W18O62であることを特徴とする、請求項12〜17のいずれか一項に記載の方法。
- 電子を伝導する前記材料が、チタン金属のスポンジ、又はカーボンフェルト若しくはファブリックであることを特徴とする、請求項12〜18のいずれか一項に記載の方法。
- 請求項1〜6に記載の触媒を使用する工程を含むことを特徴とするメタンのメタノールへの転換方法。
- CH4を、請求項1〜5、7又は8に記載の触媒と接触させる工程を含むことを特徴とするメタンのCO2への直接酸化方法。
- 請求項1〜5、7又は8に記載の触媒、又は請求項9〜11のいずれか1項に記載の電極、又は請求項12〜19のいずれか一項に記載の方法によって得られる電極を含むことを特徴とする燃料電池。
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
FR0902054 | 2009-04-28 | ||
FR0902054A FR2944716B1 (fr) | 2009-04-28 | 2009-04-28 | Catalyseur et procede d'oxydation electrochimique du methane |
PCT/FR2010/000328 WO2010125252A2 (fr) | 2009-04-28 | 2010-04-23 | Catalyseur et procede d'oxydation electrochimique du methane |
Publications (2)
Publication Number | Publication Date |
---|---|
JP2012525246A JP2012525246A (ja) | 2012-10-22 |
JP5579256B2 true JP5579256B2 (ja) | 2014-08-27 |
Family
ID=41509004
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP2012507793A Expired - Fee Related JP5579256B2 (ja) | 2009-04-28 | 2010-04-23 | メタンの電気化学的酸化のための触媒及び方法 |
Country Status (5)
Country | Link |
---|---|
US (2) | US20120088186A1 (ja) |
EP (1) | EP2424660B1 (ja) |
JP (1) | JP5579256B2 (ja) |
FR (1) | FR2944716B1 (ja) |
WO (1) | WO2010125252A2 (ja) |
Families Citing this family (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2013134076A1 (en) * | 2012-03-08 | 2013-09-12 | Viceroy Chemical Inc | Chain modification of gaseous methane using aqueous electrochemical activation at a three-phase interface |
JP2015085311A (ja) * | 2013-11-01 | 2015-05-07 | 国立大学法人広島大学 | 水素酸化触媒 |
CN103949263B (zh) * | 2014-04-27 | 2016-04-13 | 东北石油大学 | 用于甲烷制甲醇的钙钛矿复合氧化物催化剂及其制备方法 |
JP6358680B2 (ja) * | 2014-09-01 | 2018-07-18 | 国立大学法人 東京大学 | 共有結合性有機構造体を含む導電性ハイブリッド材料 |
US20180118772A1 (en) * | 2016-10-31 | 2018-05-03 | Korea Institute Of Science And Technology | Catalyst for synthesizing methanol or its precursor, method for preparing the catalyst and method for producing methanol or its precursor using the catalyst |
WO2020190874A1 (en) * | 2019-03-15 | 2020-09-24 | Massachusetts Institute Of Technology | Controlled electrochemical oxidation of pt(ii) ions for continuous methane-to-methanol conversion |
AU2022212964A1 (en) * | 2021-01-27 | 2023-09-07 | The Board Of Trustees Of The University Of Illinois | Electrochemical oxidation of methane towards methanol on mixed metal oxides |
Family Cites Families (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0616847B1 (en) * | 1993-03-26 | 1997-11-19 | Nippon Oil Co. Ltd. | Solid acid catalyst for paraffin conversion and process for paraffin conversion using the same |
JP3522824B2 (ja) * | 1993-03-26 | 2004-04-26 | 新日本石油株式会社 | パラフィンの異性化用固体酸触媒及びそれを用いるパラフィンの異性化方法 |
JP2002134122A (ja) * | 2000-10-26 | 2002-05-10 | Junichiro Otomo | メタノール燃料電池用燃料極材料及びメタノール燃料電池、並びにこれらの製造方法 |
CA2428180A1 (en) * | 2000-11-08 | 2002-05-16 | Idemitsu Kosan Co., Ltd. | Catalyst for hydrocarbon reforming and method of reforming hydrocarbon with the same |
JPWO2004045009A1 (ja) * | 2002-11-13 | 2006-04-06 | 独立行政法人産業技術総合研究所 | 燃料電池用触媒及びそれを用いた電極 |
CN1300879C (zh) * | 2004-10-20 | 2007-02-14 | 华南理工大学 | 以杂多酸为促进剂的燃料电池阳极催化剂的制备方法 |
KR20070095055A (ko) * | 2006-03-20 | 2007-09-28 | 삼성에스디아이 주식회사 | 연료 전지용 막-전극 어셈블리, 이의 제조방법 및 이를포함하는 연료 전지 시스템 |
US7910263B2 (en) * | 2006-10-26 | 2011-03-22 | Samsung Sdi Co., Ltd. | Electrode including a heteropoly acid additive for fuel cell, membrane-electrode assembly for fuel cell including same, and fuel cell system including the same |
US20080249197A1 (en) * | 2007-04-09 | 2008-10-09 | Maureen L Bricker | Process for the Production of Methanol from Methane using a Supported Transition Metal Catalyst |
US8753997B2 (en) * | 2007-05-18 | 2014-06-17 | Colorado School Of Mines | Immobilized heteropoly acids and the use of the same for electrode stabilization and enhancement |
-
2009
- 2009-04-28 FR FR0902054A patent/FR2944716B1/fr not_active Expired - Fee Related
-
2010
- 2010-04-23 WO PCT/FR2010/000328 patent/WO2010125252A2/fr active Application Filing
- 2010-04-23 US US13/318,037 patent/US20120088186A1/en not_active Abandoned
- 2010-04-23 JP JP2012507793A patent/JP5579256B2/ja not_active Expired - Fee Related
- 2010-04-23 EP EP10723164.9A patent/EP2424660B1/fr not_active Not-in-force
-
2015
- 2015-11-12 US US14/939,345 patent/US20160064743A1/en not_active Abandoned
Also Published As
Publication number | Publication date |
---|---|
WO2010125252A3 (fr) | 2010-12-23 |
WO2010125252A2 (fr) | 2010-11-04 |
US20160064743A1 (en) | 2016-03-03 |
JP2012525246A (ja) | 2012-10-22 |
EP2424660B1 (fr) | 2014-07-16 |
US20120088186A1 (en) | 2012-04-12 |
EP2424660A2 (fr) | 2012-03-07 |
FR2944716B1 (fr) | 2011-05-27 |
FR2944716A1 (fr) | 2010-10-29 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
Zhu et al. | Heteroatom-doped carbon catalysts for zinc–air batteries: progress, mechanism, and opportunities | |
Lu et al. | Highly efficient urea oxidation via nesting nano-nickel oxide in eggshell membrane-derived carbon | |
JP5579256B2 (ja) | メタンの電気化学的酸化のための触媒及び方法 | |
Chen et al. | From bimetallic metal-organic framework to porous carbon: high surface area and multicomponent active dopants for excellent electrocatalysis | |
Zhang et al. | An Fe-MOF nanosheet array with superior activity towards the alkaline oxygen evolution reaction | |
Ren et al. | Ancient chemistry “pharaoh’s snakes” for efficient Fe-/N-doped carbon electrocatalysts | |
Shao et al. | Boosting oxygen evolution by surface nitrogen doping and oxygen vacancies in hierarchical NiCo/NiCoP hybrid nanocomposite | |
Fu et al. | Metal-organic framework derived hierarchically porous nitrogen-doped carbon nanostructures as novel electrocatalyst for oxygen reduction reaction | |
Ji et al. | Hierarchical CoTe2 nanowire array: an effective oxygen evolution catalyst in alkaline media | |
Moloudi et al. | Layered double hydroxide templated synthesis of amorphous NiCoFeB as a multifunctional electrocatalyst for overall water splitting and rechargeable zinc–air batteries | |
Khalafallah et al. | Development trends on nickel‐based electrocatalysts for direct hydrazine fuel cells | |
CN105731437B (zh) | 一种异原子掺杂石墨烯及其制备方法与应用 | |
Yan et al. | Nitrogen-promoted molybdenum dioxide nanosheets for electrochemical hydrogen generation | |
Patil et al. | Self-standing SnS nanosheet array: a bifunctional binder-free thin film catalyst for electrochemical hydrogen generation and wastewater treatment | |
Kumar et al. | Iron and Nickel Phthalocyanine‐Modified Nanocarbon Materials as Cathode Catalysts for Anion‐Exchange Membrane Fuel Cells and Zinc‐Air Batteries | |
Li et al. | Facile synthesis of N, S co-doped porous carbons from a dual-ligand metal organic framework for high performance oxygen reduction reaction catalysts | |
Li et al. | Highly nitrogen-doped carbon nanotube nanoarrays as self-supported bifunctional electrocatalysts for rechargeable and flexible zinc-air batteries | |
Ma et al. | Wide-temperature-range Li–S batteries enabled by thiodimolybdate [Mo2S12] 2–as a dual-function molecular catalyst for polysulfide redox and lithium intercalation | |
Yan et al. | Large specific surface area S-doped Fe–N–C electrocatalysts derived from Metal–Organic frameworks for oxygen reduction reaction | |
Hu et al. | Synthesis of anti-poisoning spinel Mn–Co–C as cathode catalysts for low-temperature anion exchange membrane direct ammonia fuel cells | |
Nath et al. | Nanostructured copper–cobalt based spinel for the electrocatalytic H2O2 reduction reaction | |
Kaur et al. | Efficient CO2 utilization and sustainable energy conversion via aqueous Zn-CO2 batteries | |
Bocchetta et al. | Quasi-in-situ single-grain photoelectron microspectroscopy of Co/PPy nanocomposites under oxygen reduction reaction | |
Kashale et al. | Active Edge Site Exposed β‐Ni (OH) 2 Nanosheets on Stainless Steel Mesh as a Versatile Electrocatalyst for the Oxidation of Urea, Hydrazine, and Water | |
Sangamithirai et al. | Preparation and Electrochemical Characterisation of an Iron‐Nickel‐Doped Sucrose‐Derived Carbon Material for the Oxygen Evolution Reaction |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20130401 |
|
A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20131113 |
|
A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20131119 |
|
A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20140218 |
|
TRDD | Decision of grant or rejection written | ||
A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20140617 |
|
A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20140708 |
|
R150 | Certificate of patent or registration of utility model |
Ref document number: 5579256 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
LAPS | Cancellation because of no payment of annual fees |