EP2217372A1 - Procédé de production d'un catalyseur et utilisation de celui-ci comme électrocatalyseur - Google Patents
Procédé de production d'un catalyseur et utilisation de celui-ci comme électrocatalyseurInfo
- Publication number
- EP2217372A1 EP2217372A1 EP08848397A EP08848397A EP2217372A1 EP 2217372 A1 EP2217372 A1 EP 2217372A1 EP 08848397 A EP08848397 A EP 08848397A EP 08848397 A EP08848397 A EP 08848397A EP 2217372 A1 EP2217372 A1 EP 2217372A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- metal
- catalyst
- platinum group
- temperature
- platinum
- 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.)
- Withdrawn
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 104
- 239000010411 electrocatalyst Substances 0.000 title claims description 4
- 238000004519 manufacturing process Methods 0.000 title abstract description 7
- 229910052751 metal Inorganic materials 0.000 claims abstract description 91
- 239000002184 metal Substances 0.000 claims abstract description 91
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical group [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 82
- 238000000034 method Methods 0.000 claims abstract description 46
- 150000001875 compounds Chemical class 0.000 claims abstract description 18
- 239000000843 powder Substances 0.000 claims abstract description 13
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 10
- 150000002739 metals Chemical class 0.000 claims abstract description 9
- 150000003624 transition metals Chemical class 0.000 claims abstract description 8
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 111
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 46
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 23
- 239000012298 atmosphere Substances 0.000 claims description 23
- 229910052757 nitrogen Inorganic materials 0.000 claims description 23
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 22
- 239000001257 hydrogen Substances 0.000 claims description 22
- 229910052739 hydrogen Inorganic materials 0.000 claims description 22
- 239000001301 oxygen Substances 0.000 claims description 22
- 229910052760 oxygen Inorganic materials 0.000 claims description 22
- 239000000203 mixture Substances 0.000 claims description 21
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 20
- 238000000137 annealing Methods 0.000 claims description 17
- 229910052799 carbon Inorganic materials 0.000 claims description 16
- 229910052697 platinum Inorganic materials 0.000 claims description 14
- 238000002360 preparation method Methods 0.000 claims description 14
- 229910017052 cobalt Inorganic materials 0.000 claims description 11
- 239000010941 cobalt Substances 0.000 claims description 11
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 10
- 239000002904 solvent Substances 0.000 claims description 10
- 238000005984 hydrogenation reaction Methods 0.000 claims description 9
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 8
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 claims description 8
- 229910052707 ruthenium Inorganic materials 0.000 claims description 8
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 7
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 7
- 238000006356 dehydrogenation reaction Methods 0.000 claims description 7
- 230000003647 oxidation Effects 0.000 claims description 7
- 238000007254 oxidation reaction Methods 0.000 claims description 7
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 6
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 4
- 238000006555 catalytic reaction Methods 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 4
- 150000004696 coordination complex Chemical class 0.000 claims description 4
- -1 cyclopentadienyl-carbonyl Chemical group 0.000 claims description 4
- 238000005868 electrolysis reaction Methods 0.000 claims description 4
- 239000003446 ligand Substances 0.000 claims description 4
- 229910052759 nickel Inorganic materials 0.000 claims description 4
- 229910052763 palladium Inorganic materials 0.000 claims description 4
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 3
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 claims description 3
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 3
- 238000006056 electrooxidation reaction Methods 0.000 claims description 3
- POILWHVDKZOXJZ-ARJAWSKDSA-M (z)-4-oxopent-2-en-2-olate Chemical compound C\C([O-])=C\C(C)=O POILWHVDKZOXJZ-ARJAWSKDSA-M 0.000 claims description 2
- DTIGTFJLLYWKTF-UHFFFAOYSA-N 2-methylnona-2,4-diene Chemical compound CCCCC=CC=C(C)C DTIGTFJLLYWKTF-UHFFFAOYSA-N 0.000 claims description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 2
- 150000001298 alcohols Chemical class 0.000 claims description 2
- 150000007824 aliphatic compounds Chemical class 0.000 claims description 2
- 150000001336 alkenes Chemical class 0.000 claims description 2
- 150000001491 aromatic compounds Chemical class 0.000 claims description 2
- 150000001735 carboxylic acids Chemical class 0.000 claims description 2
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 2
- 150000002148 esters Chemical class 0.000 claims description 2
- 150000002391 heterocyclic compounds Chemical class 0.000 claims description 2
- 125000002462 isocyano group Chemical group *[N+]#[C-] 0.000 claims description 2
- 239000002480 mineral oil Substances 0.000 claims description 2
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 2
- 150000002902 organometallic compounds Chemical class 0.000 claims description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 2
- 239000005922 Phosphane Substances 0.000 claims 1
- 125000003118 aryl group Chemical group 0.000 claims 1
- 125000002560 nitrile group Chemical group 0.000 claims 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims 1
- 229910000064 phosphane Inorganic materials 0.000 claims 1
- 239000000446 fuel Substances 0.000 description 18
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 10
- 239000000463 material Substances 0.000 description 10
- 238000001035 drying Methods 0.000 description 8
- 229910045601 alloy Inorganic materials 0.000 description 7
- 239000000956 alloy Substances 0.000 description 7
- 238000005259 measurement Methods 0.000 description 7
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 6
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 6
- 239000006229 carbon black Substances 0.000 description 6
- 235000019241 carbon black Nutrition 0.000 description 6
- 239000003792 electrolyte Substances 0.000 description 6
- 239000007789 gas Substances 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical group CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 4
- 229910002848 Pt–Ru Inorganic materials 0.000 description 4
- 238000005470 impregnation Methods 0.000 description 4
- 239000012528 membrane Substances 0.000 description 4
- 210000004379 membrane Anatomy 0.000 description 4
- 125000002524 organometallic group Chemical group 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- 229910002837 PtCo Inorganic materials 0.000 description 3
- 229910052786 argon Inorganic materials 0.000 description 3
- 229940075397 calomel Drugs 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical compound Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 3
- 150000002170 ethers Chemical class 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 229910001092 metal group alloy Inorganic materials 0.000 description 3
- 239000002923 metal particle Substances 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- 229920000557 Nafion® Polymers 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 229910021393 carbon nanotube Inorganic materials 0.000 description 2
- 239000002041 carbon nanotube Substances 0.000 description 2
- 239000000969 carrier Substances 0.000 description 2
- 239000012876 carrier material Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 230000001419 dependent effect Effects 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 239000004530 micro-emulsion Substances 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 229940078552 o-xylene Drugs 0.000 description 2
- 238000005240 physical vapour deposition Methods 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 239000011164 primary particle Substances 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 229910052703 rhodium Inorganic materials 0.000 description 2
- 239000010948 rhodium Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 2
- 229910001887 tin oxide Inorganic materials 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- RMGHERXMTMUMMV-UHFFFAOYSA-N 2-methoxypropane Chemical compound COC(C)C RMGHERXMTMUMMV-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- 241000218213 Morus <angiosperm> Species 0.000 description 1
- 239000011865 Pt-based catalyst Substances 0.000 description 1
- 229910002849 PtRu Inorganic materials 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000003426 co-catalyst Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 150000004292 cyclic ethers Chemical class 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- POLCUAVZOMRGSN-UHFFFAOYSA-N dipropyl ether Chemical compound CCCOCCC POLCUAVZOMRGSN-UHFFFAOYSA-N 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000001493 electron microscopy Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 239000005414 inactive ingredient Substances 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000003273 ketjen black Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000010907 mechanical stirring Methods 0.000 description 1
- 150000001247 metal acetylides Chemical class 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 229910000476 molybdenum oxide Inorganic materials 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 description 1
- 238000005839 oxidative dehydrogenation reaction Methods 0.000 description 1
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 238000002161 passivation Methods 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 1
- CFQCIHVMOFOCGH-UHFFFAOYSA-N platinum ruthenium Chemical compound [Ru].[Pt] CFQCIHVMOFOCGH-UHFFFAOYSA-N 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 238000012552 review Methods 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000010944 silver (metal) Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 229910001930 tungsten oxide Inorganic materials 0.000 description 1
- 238000001771 vacuum deposition Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 238000007704 wet chemistry method Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
- B01J37/086—Decomposition of an organometallic compound, a metal complex or a metal salt of a carboxylic acid
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/92—Chemical or biological purification of waste gases of engine exhaust gases
- B01D53/94—Chemical or biological purification of waste gases of engine exhaust gases by catalytic processes
- B01D53/9445—Simultaneously removing carbon monoxide, hydrocarbons or nitrogen oxides making use of three-way catalysts [TWC] or four-way-catalysts [FWC]
- B01D53/945—Simultaneously removing carbon monoxide, hydrocarbons or nitrogen oxides making use of three-way catalysts [TWC] or four-way-catalysts [FWC] characterised by a specific catalyst
-
- 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
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
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- 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
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/46—Ruthenium, rhodium, osmium or iridium
- B01J23/462—Ruthenium
-
- 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
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- 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
- B01J35/391—Physical properties of the active metal ingredient
- B01J35/393—Metal or metal oxide crystallite size
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- 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
- B01J37/04—Mixing
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- 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
- H01M4/921—Alloys or mixtures with metallic elements
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- 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
- H01M4/925—Metals of platinum group supported on carriers, e.g. powder carriers
- H01M4/926—Metals of platinum group supported on carriers, e.g. powder carriers on carbon or graphite
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2255/00—Catalysts
- B01D2255/10—Noble metals or compounds thereof
- B01D2255/102—Platinum group metals
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2255/00—Catalysts
- B01D2255/20—Metals or compounds thereof
- B01D2255/207—Transition metals
- B01D2255/20746—Cobalt
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2255/00—Catalysts
- B01D2255/20—Metals or compounds thereof
- B01D2255/207—Transition metals
- B01D2255/20753—Nickel
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2255/00—Catalysts
- B01D2255/70—Non-metallic catalysts, additives or dopants
- B01D2255/702—Carbon
-
- 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
- B01J2235/00—Indexing scheme associated with group B01J35/00, related to the analysis techniques used to determine the catalysts form or properties
- B01J2235/15—X-ray diffraction
-
- 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
- B01J2235/00—Indexing scheme associated with group B01J35/00, related to the analysis techniques used to determine the catalysts form or properties
- B01J2235/30—Scanning electron microscopy; Transmission electron microscopy
-
- 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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1009—Fuel cells with solid electrolytes with one of the reactants being liquid, solid or liquid-charged
- H01M8/1011—Direct alcohol fuel cells [DAFC], e.g. direct methanol fuel cells [DMFC]
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- 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
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters
-
- 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
- Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
- Y02T10/00—Road transport of goods or passengers
- Y02T10/10—Internal combustion engine [ICE] based vehicles
- Y02T10/12—Improving ICE efficiencies
Definitions
- the invention relates to a process for the preparation of a catalyst comprising a metal of the platinum group and a second metal selected from the metals of the platinum group or of the transition metals.
- the invention further relates to a use of the catalyst according to the invention.
- Catalysts containing an alloy of at least two different metals, where at least one metal is a metal of the platinum group are used e.g. used as electrocatalysts in fuel cells.
- such catalysts are suitable for use as cathode catalyst in direct methanol fuel cells (direct methanol fuel cells, DMFC).
- direct methanol fuel cells direct methanol fuel cells, DMFC.
- cathode catalysts in DMFCs In addition to a high current density for the reduction of oxygen, further requirements are placed on cathode catalysts in DMFCs. Since a methanol passage through a membrane used as a separator in principle allows the catalytic oxidation of methanol with oxygen at the cathode, it is necessary that the cathode catalyst used is as inactive as possible against the methanol oxidation. That is, it must have a high selectivity for the oxygen reduction over the methanol oxidation.
- Temperature-treated porphyrin-transition metal complexes e.g. from J. Applied Electrochemistry (1998), pp. 673-682, or transition metal sulfides, for example ReRuS or MoRuS systems, as described e.g. from J. Electrochem. Soc, 145 (10), 1998, pages 3463-3471, see e.g. a high current density for the oxygen reduction and show a good tolerance to methanol.
- these catalysts do not achieve the activity of Pt-based catalysts and are also not stable enough to ensure a sufficient current density in the acidic environment of a fuel cell for a long time.
- Pt catalysts which are alloyed with transition metals, have a good methanol tolerance and ensure a sufficiently high current density for the oxygen reduction.
- an active methanol-tolerant cathode catalyst should have the highest possible oxygen binding energy with simultaneously low hydrogen binding energy.
- a high oxygen-binding energy ensures a high current density for the reduction of oxygen, while a low hydrogen-binding energy attenuates the electro-oxidative dehydrogenation of methanol to carbon monoxide and thus increases the methanol tolerance.
- Suitable processes include impregnation of carbon carriers with metal-containing precursors, application of colloidal Carrier metal alloy particles and the synthesis of highly dispersed metal particles in microemulsions
- the application of colloidal metal alloy particles to supports and the synthesis of highly dispersed metal particles in microemulsions require the use of very expensive starting materials, eg surfactants
- the disadvantage of impregnation is that it is generally difficult to control the size of nanoparticles and their distribution, and the use of high-boiling solvents, as is often the case during impregnation, is i ke problematic in the production of technically relevant amounts of catalyst.
- a platinum catalyst is first prepared in a first step. After filtration, washing and drying, this is again a liquid reaction medium, generally water, dispersed. To the dispersion, the element to be incorporated is added in the form of a suitable soluble salt and precipitated with a suitable precipitant, preferably sodium carbonate. The resulting dispersion is filtered, the separated solid washed, dried and then subjected to a high-temperature treatment under a reducing atmosphere. Disadvantage of this method, however, is that a once filtered once, washed and dried product must be subjected a second time to this sequence of processing steps.
- the object is achieved by a process for the preparation of a catalyst comprising a metal of the platinum group and a second metal selected from the metals of the platinum group or of the transition metals, which comprises the following steps:
- the compound obtained by the annealing in step (b) is generally an alloy.
- step (a) By mixing the catalyst containing the metal of the platinum group with the complex compound containing the second metal to a dry powder in step (a), it is avoided that the already washed and dried catalyst containing the metal of the platinum group contains, again filtered, washed and dried. All that is done is the high temperature annealing treatment in step (b) to obtain the alloy.
- step (b) the high temperature annealing treatment
- the catalyst containing the metal of the platinum group is, in a first embodiment, a pure metal which is in powder form. In an alternative embodiment, the catalyst containing the metal of the platinum group is supported.
- the carrier used here is generally a catalytically inactive material on which the catalytically active material is applied or which contains the catalytic material.
- the metal of the platinum group is rhodium, iridium, nickel, palladium, platinum, copper, silver, gold.
- the platinum group metal is platinum.
- the metal of the platinum group is preferably present as a powder having a particle size in the range of 1 to 200 microns.
- the metal of the platinum group has primary particle sizes in the range of 2 to 20 nm.
- the powder of platinum group metal may also contain other catalytically inactive ingredients. These serve e.g. as a release agent.
- all materials which could also be used as catalyst supports are suitable for this purpose.
- carbon is generally used as the support.
- the carbon may e.g. as activated carbon, carbon black or nanostructured carbon. Suitable carbon blacks include, for example, Vulcan XC72 or Ketjen Black EC300. When the carbon is nanostructured carbon, carbon nanotubes are preferred.
- the metal of the platinum group is bonded to the support material. The preparation of such supported or unsupported catalysts containing a metal of the platinum group is known and corresponding catalysts can be obtained commercially.
- the second metal contained in the complex compound preferably an organometallic complex compound, selected from the metals of the platinum group or the transition metals is preferably selected from the group consisting of ruthenium, cobalt, nickel and palladium.
- the second metal is present as an organometallic complex compound.
- Preferred ligands for forming the organometallic complex compound are olefins, preferably dimethyloctadiene, aromatics, preferably pyridine, 2,4-pentanedione.
- the second metal is in the form of a mixed cyclopentadienyl Carbonyl complex or as a pure or mixed carbonyl, phosphine, cyano or Isocyano complex is present.
- the second metal is present as an organometallic complex compound with acetylacetonate or 2,4-pentanedione as ligand.
- the second metal is preferably ionic.
- the complex containing the second metal is dry , Alternatively, however, it is also possible that the complex compound is dissolved in a solvent.
- the solvent is preferably selected from the group consisting of hexane, cyclohexane, toluene and ether compounds.
- Preferred ether compounds are open-chain ethers, for example diethyl ether, di-n-propyl ether or 2-methoxypropane, and also cyclic ethers, such as tetrahydrofuran or 1,4-dioxane.
- the mixture of the catalyst containing the platinum group metal and the organometallic compound or metal complex is dried before annealing in step (b).
- the drying can be carried out at ambient temperature or at an elevated temperature. When drying takes place at elevated temperature, the temperature is preferably above the boiling point of the solvent.
- the drying time is chosen so that after drying, the proportion of solvents in the mixture of the catalyst containing the metal of the platinum group and the complex compound less than 5 wt .-%, preferably less than 2 wt .-% is ,
- Suitable solids mixers usually include a container in which the material to be mixed is agitated.
- Suitable solid mixers are e.g. Paddle mixers, screw mixers, silo or pneumatic mixers.
- a container is used in which fast rotating blades or blades are included.
- a device is eg an Ultra-Turrax®.
- the powder produced by the mixture in step (a) is tempered.
- Annealing is preferably performed in at least two steps at different temperatures, with the temperature being increased from step to step.
- the complex compound By annealing, the complex compound is decomposed and the metal bound in it is released.
- the metal combines with the metal of the platinum group.
- the result is an alloy in which each metal crystallites are disordered next to each other.
- the individual metal crystallites generally have a size in the range of 2 to 7 nm.
- the annealing is carried out in three steps, the first step being at a substantially constant temperature in the range of 90 to 140 ° C., preferably in the range of 100 to 110 ° C. and a duration of 90 to 180 minutes, preferably in the range of 100 to 150 minutes.
- the second step takes place at a substantially constant temperature in the range between 300 and 350 ° C. and a duration of 3 to 5 hours, preferably at a duration in the range of 3.5 to 4.5 hours.
- the temperature at which the second step is carried out depends on the second metal used. If, for example, cobalt is used as the second metal, the second step is preferably carried out at a temperature in the range from 200 to 240 ° C., preferably at substantially 210 ° C. If ruthenium is used as the second metal, the second step is preferably carried out at a temperature in the range from 290 to 310 ° C., preferably at substantially 300 ° C.
- the third step is preferably carried out at a substantially constant temperature in the range between 500 and 800 ° C. for a duration in the range from 20 minutes to 4 hours.
- the temperature and the duration of the third step are in turn dependent on the second metal used.
- the third step is carried out, for example, when using cobalt as the second metal at a temperature in the range of 580 to 620 0 C and a duration of 2.5 to 3.5 hours.
- the third step is carried out at a temperature of substantially 600 ° C. for substantially 3 hours.
- the third step takes place at a temperature of tured in the range 680 to 720 0 C for a period of 20 to 40 minutes. Platinum is used here as the metal of the platinum group.
- the temperature between the individual steps is preferably increased in a linearly increasing manner.
- the temperature increase from the first to the second step preferably requires within 20 to 60 minutes and the temperature increase from the second to the third step within 2 to 4 hours, preferably within 2.5 to 3.5 hours.
- the first step of the annealing process is preferably carried out under an inert atmosphere.
- the inert atmosphere is preferably a nitrogen atmosphere.
- the nitrogen e.g. Argon is used.
- nitrogen is preferred.
- the at least one step following the first step is preferably carried out under a reducing atmosphere.
- the reducing atmosphere preferably contains hydrogen.
- the proportion of hydrogen is dependent on the composition of the catalyst produced.
- the second step is preferably carried out under an atmosphere containing hydrogen and nitrogen in substantially equal parts.
- the third step of the annealing process is carried out under an atmosphere in which hydrogen and nitrogen are preferably present in a ratio of 1: 9.
- both the second and third annealing steps are preferably conducted under an atmosphere in which hydrogen and nitrogen are in a ratio of 2: 1.
- step (b) After completion of the annealing in step (b), preferably, it is cooled to ambient temperature under an inert atmosphere.
- the inert atmosphere is also, as already described above, preferably a nitrogen atmosphere or an argon atmosphere. It is also possible to use a mixture of nitrogen and argon.
- the thermally treated Catalyst is preferably slurried in sulfuric acid and stirred under a nitrogen atmosphere.
- sulfuric acid preferably 0 to 1 M, preferably 0.4 to 0.6 M sulfuric acid is used.
- the temperature is in the range between 60 and 100 0 C, preferably between 85 and 95 0 C.
- the duration of the process is preferably in the range of 30 to 90 minutes, preferably between 50 and 70 minutes.
- the catalyst is washed, filtered and dried. The drying is preferably carried out under vacuum.
- the catalyst prepared according to the invention is stable to acids and has a high current density for oxygen reduction, as desired in direct methanol fuel cells.
- the catalyst prepared according to the invention is also very tolerant to methanol impurities.
- the catalyst has a large specific surface area. This is preferably achieved in that the catalyst contains a carrier, wherein the alloy of the metal of the platinum group and the second metal is applied to the carrier. To achieve a large surface area, it is preferred if the support is porous.
- the catalyst When the catalyst is supported on the carrier, individual particles of the catalyst material are generally contained on the carrier surface. Usually, the catalyst is not present as a continuous layer on the support surface.
- Suitable carriers are e.g. Ceramics or carbon. Particularly preferred as carrier material is carbon.
- the advantage of carbon as a carrier material is that it is electrically conductive.
- the catalyst is used as an electrocatalyst in a fuel cell, e.g. As the cathode of the fuel cell is used, it is necessary that it is electrically conductive to ensure the function of the fuel cell.
- Tin oxide preferably semiconducting tin oxide, ⁇ -alumina, which is optionally C-coated, titanium dioxide, zirconium dioxide, silicon dioxide, the latter preferably being highly dispersed, wherein the primary particles have a diameter of 50-200 nm.
- tungsten oxide and molybdenum oxide which are also present as bronzes, ie as substoichiometric oxide.
- carbon When carbon is used as the material for the carrier, it is preferably present as carbon black or graphite. Alternatively, the carbon may be present as activated carbon or as so-called nanostructured carbon. A representative of the nanostructured carbons are e.g. Carbon nanotubes.
- the metal of the platinum group is first deposited on the support. This is generally done in solution.
- Metal compounds be dissolved in a solvent.
- the metal can be bound covalently, ionically or complexed.
- the metal is deposited reductively, as a precursor or alkaline by precipitation of the corresponding hydroxide.
- Further possibilities for depositing the metal of the platinum group are also impregnations with a solution containing the metal (Incipient Wetness), Chemical Vacuum Deposition (CVD) or Physical Vapor Deposition (PVD) methods and all other methods known to the person skilled in the art with which a metal can be deposited.
- a salt of the metal of the platinum group is first precipitated. After precipitation, drying and temperature treatment are carried out to prepare the catalyst containing the metal of the platinum group.
- the catalyst prepared by the process according to the invention is suitable, for example, for use as electrode material in a fuel cell.
- Other suitable applications include the electro-oxidation of methanol or hydrogen outside of fuel cells, the electroreduction of oxygen, chloralkali electrolysis and water electrolysis.
- the catalyst prepared by the process according to the invention for example in auto exhaust gas catalysis, for example as a 3-way catalyst or diesel oxidation catalyst, or for catalytic hydrogenation or dehydrogenation in the chemical industry. These include, for example, hydrogenations of unsaturated aliphatic, aromatic and heterocyclic compounds.
- the catalyst prepared by the process of the invention is used for an electrode in a direct methanol fuel cell.
- the electrode for which the catalyst is used is, in particular, a cathode of the direct methanol fuel cell.
- the catalyst produced by the process of the invention When used as the cathode of a direct methanol fuel cell, the catalyst produced by the process of the invention exhibits a sufficiently high current density for the oxygen reduction.
- the catalyst prepared by the process according to the invention is tolerant of methanol impurities. This means that the catalyst prepared by the process according to the invention is substantially inactive compared to the methanol oxidation.
- the thermally treated catalyst was then slurried with 0.5 MH 2 SO 4 and stirred under nitrogen for one hour at 90 0 C. The catalyst was then filtered off with suction and dried under vacuum.
- the catalyst prepared in this way contains 52% by weight of platinum, 18.2% by weight of cobalt.
- the crystallite size was determined by X-ray diffractometry. This gives a crystal size of 4.2 nm.
- the gas atmosphere was unchanged composed of nitrogen and hydrogen in a ratio of 1: 2. After 3 hours at a temperature of 600 0 C was cooled under a nitrogen atmosphere. Once room temperature has been reached, it was switched to air atmosphere. No temperature increase was observed in the product.
- the catalyst was subjected to a wash with 0.5 molar H 2 SO 4 at a temperature of 90 ° C. for one hour. Subsequently, the catalyst was washed, filtered and dried.
- the catalyst thus prepared has a platinum content of 48.4 wt .-%, the cobalt content was 21, 2 wt .-% and determined by X-ray diffractometry crystallite size was 3.1 nm.
- the mixture was kept for 2 hours at a temperature of 1 10 0 C under nitrogen atmosphere. Subsequently, the temperature was raised to 300 0 C within 30 minutes. The mixture was then held at this temperature for 4 hours.
- the gas atmosphere used was a mixture of hydrogen and nitrogen in the ratio of 1: 1. Subsequently, the gas atmosphere was changed to a ratio of hydrogen to nitrogen of 1: 9. The temperature was raised to 700 0 C within 3 hours and then held at 700 0 C for 30 minutes. This was followed by a cooling under a nitrogen atmosphere.
- the catalyst for passivation was treated for each 30 minutes first with 0.1% oxygen, then with 0.5% oxygen, with 1% oxygen and with 5% oxygen, each in nitrogen before each expansion.
- the catalyst thus prepared contains 37% by weight of ruthenium, 23% by weight of cobalt.
- the crystallite size is 3.3 nm and the lattice constant (XRD) is 0.386 nm.
- XRD lattice constant
- the catalysts prepared according to the Comparative Example and Preparation Example 1 were made into an ink. To this was added 6 mg of catalyst, 1 g of H 2 O, 0.1 g of 5% strength Nafion solution (in alcohol / water mixture) and 7.07 g of isopropanol. mixed. The experiments were carried out in a 3-electrode arrangement with a calomel reference electrode on an annular disc electrode. For the coating, 200 ⁇ l of the ink in 20 ⁇ l portions were applied to the measuring head with an area of 100 mm 2 and dried with a hot air dryer. The experiments were carried out in 1 molar sulfuric acid at 70 0 C. Before starting the measurement, the electrolyte was saturated with oxygen for one hour.
- a current density for the oxygen reduction without MeOH of 34.7 mA / mg Pt for the current density for the oxygen reduction in the presence of methanol of 32.3 mA / mg Pt.
- a current density for the oxygen reduction of 39.7 mA / mg Pt without methanol and of 32.3 mA / mg Pt for the oxygen reduction in the presence of methanol shows that the current densities are greater for the catalyst according to the invention than for the catalyst prepared according to the prior art.
- an ink was first prepared from 80 mg of catalyst.
- the catalyst was mixed with 2 g of water and 2 g of 5 percent Nafi- on caps in ethanol and processed in the ultrasonic bath with the addition of a few 3 mm glass beads for one hour to a homogeneous suspension.
- the catalyst-containing ink was then applied to the measuring head of a rotating disk electrode and dried in an unheated air stream. When coating the Disc electrodes were dry applied between 100 and 150 ⁇ g of catalyst. The exact amount of catalyst was obtained by back weighing the disk electrode.
- a 3-electrode arrangement was used, comprising a working electrode, a counterelectrode and a reference electrode.
- the potentiostatic measurement was carried out with a Jaissle device (PGU 10V-1A-E).
- PGU 10V-1A-E Jaissle device
- the working electrode was rotated at a constant frequency of 1600 rpm.
- the potential was cycled 5 times between 50 mV and 500 mV compared to a normal hydrogen electrode with a scan rate of 20 mV / s.
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Abstract
L'invention concerne un procédé de production d'un catalyseur contenant un métal du groupe platine, ainsi qu'un second métal choisi parmi les métaux du groupe platine ou les métaux de transition. Ce procédé consiste à mélanger, dans une première étape, un catalyseur contenant le métal du groupe platine avec un complexe contenant le second métal pour former une poudre sèche, puis à recuire la poudre afin de former une liaison entre le métal du groupe platine et le second métal. L'invention concerne en outre l'utilisation du catalyseur obtenu par le procédé décrit.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP08848397A EP2217372A1 (fr) | 2007-11-09 | 2008-11-06 | Procédé de production d'un catalyseur et utilisation de celui-ci comme électrocatalyseur |
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP07120359 | 2007-11-09 | ||
PCT/EP2008/065039 WO2009060019A1 (fr) | 2007-11-09 | 2008-11-06 | Procédé de production d'un catalyseur et utilisation de celui-ci comme électrocatalyseur |
EP08848397A EP2217372A1 (fr) | 2007-11-09 | 2008-11-06 | Procédé de production d'un catalyseur et utilisation de celui-ci comme électrocatalyseur |
Publications (1)
Publication Number | Publication Date |
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EP2217372A1 true EP2217372A1 (fr) | 2010-08-18 |
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Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
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EP08848397A Withdrawn EP2217372A1 (fr) | 2007-11-09 | 2008-11-06 | Procédé de production d'un catalyseur et utilisation de celui-ci comme électrocatalyseur |
Country Status (8)
Country | Link |
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US (1) | US8293675B2 (fr) |
EP (1) | EP2217372A1 (fr) |
JP (1) | JP5579071B2 (fr) |
KR (1) | KR101541207B1 (fr) |
CN (1) | CN101990462A (fr) |
CA (1) | CA2704667A1 (fr) |
RU (1) | RU2010123285A (fr) |
WO (1) | WO2009060019A1 (fr) |
Families Citing this family (19)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
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EP2417059B1 (fr) | 2009-04-06 | 2014-12-10 | Basf Se | Procédé de transformation de gaz naturel en hydrocarbures aromatiques, avec séparation électrochimique d'hydrogène |
JP2012526741A (ja) | 2009-05-14 | 2012-11-01 | ビーエーエスエフ ソシエタス・ヨーロピア | 芳香族アミンの製造方法 |
EP2437883A2 (fr) * | 2009-06-02 | 2012-04-11 | Basf Se | Catalyseur pour applications électrochimiques |
JP5471252B2 (ja) * | 2009-09-30 | 2014-04-16 | 国立大学法人北海道大学 | 合金化度と分散性を制御したPtRu/C触媒及びその製造方法 |
JP5660917B2 (ja) * | 2011-02-04 | 2015-01-28 | 国立大学法人東京工業大学 | 燃料電池用空気極触媒とその製造方法 |
WO2013182535A1 (fr) | 2012-06-06 | 2013-12-12 | Basf Se | Procédé de production de catalyseurs à base de métaux de transitions dopés à l'azote et leur utilisation dans l'oxydation électrochimique de composés de soufre (iv) |
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BR112016026174B1 (pt) | 2014-05-16 | 2021-10-13 | Dow Global Technologies Llc | Processo para preparação de um catalisador de síntese de fischer-tropsch |
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EP3528943A1 (fr) * | 2016-10-20 | 2019-08-28 | Basf Se | Procédé de production d'un catalyseur comprenant un composé intermétallique et catalyseur produit avec ce procédé |
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KR102468470B1 (ko) * | 2020-12-09 | 2022-11-18 | 비나텍주식회사 | 연료전지용 백금계 합금 촉매의 제조 방법 |
KR102466103B1 (ko) * | 2020-12-18 | 2022-11-11 | 비나텍주식회사 | 연료전지용 백금계 합금 촉매의 제조 방법 |
KR102459158B1 (ko) * | 2020-12-18 | 2022-10-26 | 비나텍주식회사 | 코발트를 함유하는 연료전지용 백금계 합금 촉매의 제조 방법 |
CN113437318A (zh) * | 2021-06-25 | 2021-09-24 | 北京大学 | 一种碳负载的贵金属合金纳米颗粒及其制备方法和应用 |
CN115863678A (zh) * | 2022-12-20 | 2023-03-28 | 佛山仙湖实验室 | 一种富含缺陷的铂基纳米片催化剂及其制备方法和应用 |
Family Cites Families (12)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR2628417B1 (fr) * | 1988-03-08 | 1990-07-27 | Rhone Poulenc Sante | Procede de preparation d'alcools insatures |
US5916702A (en) * | 1997-08-15 | 1999-06-29 | Exxon Research And Engineering Co. | CO tolerant platinum-zinc fuel cell electrode |
JP2001198469A (ja) * | 1999-11-05 | 2001-07-24 | Sekisui Chem Co Ltd | 水素貯蔵・供給用金属担持触媒及びこれを利用した水素貯蔵・供給システム |
JP2002095969A (ja) * | 2000-09-21 | 2002-04-02 | Ishifuku Metal Ind Co Ltd | 白金−コバルト合金触媒の製造方法 |
US7157401B2 (en) * | 2002-10-17 | 2007-01-02 | Carnegie Mellon University | Catalyst for the treatment of organic compounds |
US20040101718A1 (en) * | 2002-11-26 | 2004-05-27 | Lixin Cao | Metal alloy for electrochemical oxidation reactions and method of production thereof |
KR100506091B1 (ko) | 2003-02-19 | 2005-08-04 | 삼성에스디아이 주식회사 | 연료전지의 캐소드용 촉매 |
US7208437B2 (en) * | 2004-01-16 | 2007-04-24 | T/J Technologies, Inc. | Catalyst and method for its manufacture |
US7335245B2 (en) * | 2004-04-22 | 2008-02-26 | Honda Motor Co., Ltd. | Metal and alloy nanoparticles and synthesis methods thereof |
JP4490201B2 (ja) * | 2004-08-04 | 2010-06-23 | Dowaホールディングス株式会社 | 凹凸表面をもつ微細な合金粒子粉末およびその製造法 |
JP4390693B2 (ja) * | 2004-12-17 | 2009-12-24 | 富士通株式会社 | 燃料電池用触媒の製造方法および燃料電池の製造方法 |
US7507495B2 (en) * | 2004-12-22 | 2009-03-24 | Brookhaven Science Associates, Llc | Hydrogen absorption induced metal deposition on palladium and palladium-alloy particles |
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2008
- 2008-11-06 CN CN200880124347XA patent/CN101990462A/zh active Pending
- 2008-11-06 US US12/742,026 patent/US8293675B2/en not_active Expired - Fee Related
- 2008-11-06 CA CA2704667A patent/CA2704667A1/fr not_active Abandoned
- 2008-11-06 WO PCT/EP2008/065039 patent/WO2009060019A1/fr active Application Filing
- 2008-11-06 KR KR1020107012730A patent/KR101541207B1/ko not_active IP Right Cessation
- 2008-11-06 EP EP08848397A patent/EP2217372A1/fr not_active Withdrawn
- 2008-11-06 RU RU2010123285/04A patent/RU2010123285A/ru unknown
- 2008-11-06 JP JP2010532584A patent/JP5579071B2/ja not_active Expired - Fee Related
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US20100267551A1 (en) | 2010-10-21 |
RU2010123285A (ru) | 2011-12-20 |
US8293675B2 (en) | 2012-10-23 |
KR20100099160A (ko) | 2010-09-10 |
CA2704667A1 (fr) | 2009-05-14 |
KR101541207B1 (ko) | 2015-07-31 |
JP2011502758A (ja) | 2011-01-27 |
CN101990462A (zh) | 2011-03-23 |
JP5579071B2 (ja) | 2014-08-27 |
WO2009060019A1 (fr) | 2009-05-14 |
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