DE2125590A1 - Metal anthraquinone cyanines - useful as electrocatalysts in fuel cells - Google Patents
Metal anthraquinone cyanines - useful as electrocatalysts in fuel cellsInfo
- Publication number
- DE2125590A1 DE2125590A1 DE19712125590 DE2125590A DE2125590A1 DE 2125590 A1 DE2125590 A1 DE 2125590A1 DE 19712125590 DE19712125590 DE 19712125590 DE 2125590 A DE2125590 A DE 2125590A DE 2125590 A1 DE2125590 A1 DE 2125590A1
- Authority
- DE
- Germany
- Prior art keywords
- metal complexes
- fuel cells
- electrocatalysts
- metal
- iron
- 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.)
- Granted
Links
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 28
- 239000002184 metal Substances 0.000 title claims abstract description 28
- 239000000446 fuel Substances 0.000 title claims abstract description 9
- 239000010411 electrocatalyst Substances 0.000 title claims abstract description 7
- PYKYMHQGRFAEBM-UHFFFAOYSA-N anthraquinone Natural products CCC(=O)c1c(O)c2C(=O)C3C(C=CC=C3O)C(=O)c2cc1CC(=O)OC PYKYMHQGRFAEBM-UHFFFAOYSA-N 0.000 title description 3
- 150000004056 anthraquinones Chemical class 0.000 title description 3
- 229910052742 iron Inorganic materials 0.000 claims abstract description 8
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 7
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 5
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical group [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 15
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 12
- 229910017052 cobalt Inorganic materials 0.000 claims description 6
- 239000010941 cobalt Substances 0.000 claims description 6
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 6
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims description 5
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 4
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 4
- 239000011651 chromium Substances 0.000 claims description 4
- 239000011701 zinc Substances 0.000 claims description 4
- 125000003277 amino group Chemical group 0.000 claims 1
- 150000003839 salts Chemical class 0.000 abstract description 2
- 229910052748 manganese Inorganic materials 0.000 abstract 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 abstract 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 6
- 239000003054 catalyst Substances 0.000 description 6
- -1 metal complex compounds Chemical class 0.000 description 6
- 239000001301 oxygen Substances 0.000 description 6
- 229910052760 oxygen Inorganic materials 0.000 description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 5
- 239000003792 electrolyte Substances 0.000 description 5
- 150000004696 coordination complex Chemical class 0.000 description 4
- 150000004698 iron complex Chemical class 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- 239000011148 porous material Substances 0.000 description 4
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000004020 conductor Substances 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 238000005470 impregnation Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- ANRHNWWPFJCPAZ-UHFFFAOYSA-M thionine Chemical compound [Cl-].C1=CC(N)=CC2=[S+]C3=CC(N)=CC=C3N=C21 ANRHNWWPFJCPAZ-UHFFFAOYSA-M 0.000 description 2
- KMHSUNDEGHRBNV-UHFFFAOYSA-N 2,4-dichloropyrimidine-5-carbonitrile Chemical compound ClC1=NC=C(C#N)C(Cl)=N1 KMHSUNDEGHRBNV-UHFFFAOYSA-N 0.000 description 1
- GVMVNJYLDIAZCJ-UHFFFAOYSA-N 5,8-diamino-9,10-dioxoanthracene-1,6-dicarbonitrile Chemical compound O=C1C2=CC=CC(C#N)=C2C(=O)C2=C1C(N)=C(C#N)C=C2N GVMVNJYLDIAZCJ-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
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 150000003841 chloride salts Chemical class 0.000 description 1
- VNNRSPGTAMTISX-UHFFFAOYSA-N chromium nickel Chemical compound [Cr].[Ni] VNNRSPGTAMTISX-UHFFFAOYSA-N 0.000 description 1
- 150000001868 cobalt Chemical class 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000006056 electrooxidation reaction Methods 0.000 description 1
- 238000010285 flame spraying Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 238000007731 hot pressing Methods 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 229910000358 iron sulfate Inorganic materials 0.000 description 1
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910000371 mercury(I) sulfate Inorganic materials 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 239000012860 organic pigment Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical class N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 description 1
- 238000007750 plasma spraying Methods 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 239000004449 solid propellant Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 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
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
- H01M4/9008—Organic or organo-metallic compounds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F13/00—Compounds containing elements of Groups 7 or 17 of the Periodic Table
- C07F13/005—Compounds without a metal-carbon linkage
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
- C07F15/02—Iron compounds
- C07F15/025—Iron compounds without a metal-carbon linkage
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
- C07F15/04—Nickel compounds
- C07F15/045—Nickel compounds without a metal-carbon linkage
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
- C07F15/06—Cobalt compounds
- C07F15/065—Cobalt compounds without a metal-carbon linkage
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B47/00—Porphines; Azaporphines
- C09B47/04—Phthalocyanines abbreviation: Pc
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B47/00—Porphines; Azaporphines
- C09B47/04—Phthalocyanines abbreviation: Pc
- C09B47/045—Special non-pigmentary uses, e.g. catalyst, photosensitisers of phthalocyanine dyes or pigments
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B5/00—Dyes with an anthracene nucleus condensed with one or more heterocyclic rings with or without carbocyclic rings
- C09B5/24—Dyes with an anthracene nucleus condensed with one or more heterocyclic rings with or without carbocyclic rings the heterocyclic rings being only condensed with an anthraquinone nucleus in 1-2 or 2-3 position
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B57/00—Other synthetic dyes of known constitution
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Inert Electrodes (AREA)
- Catalysts (AREA)
Abstract
Description
Metallkomplexe Vorliegende Erfindung betrifft neue Metall-Anthrachinoncyanine und ihre Verwendung als Elektrokatalysatoren in Brennstoffzellen, insbesondere für Kathoden. Metal Complexes The present invention relates to new metal anthraquinone cyanines and their use as electrocatalysts in fuel cells, especially for Cathodes.
Es ist bekannt (R. Jasinski, Nature 201, 1212 - 1213 (1964)), daß Metallphthalocyanine als Katalysatoren in Sauerstoffkathoden von Brennstoffzellen verwendet werden können. Gegenüber den üblicherweise verwendeten Edelmetallkatalysatoren (Pt, Ag) stellen diese organischen Pigmente eine sehr interessante Alternative dar.It is known (R. Jasinski, Nature 201, 1212-1213 (1964)) that Metal phthalocyanines as catalysts in oxygen cathodes of fuel cells can be used. Compared to the noble metal catalysts commonly used (Pt, Ag) these organic pigments represent a very interesting alternative.
Gemäß einem eigenen, nicht zum Stande der Technik gehörenden Vorschlag weisen Kathoden von Brennstoffzellen ein verbessertes Stromspannungsverhalten auf, wenn die Kathode und/oder der Katholyt Metallkomplexe der allgemeinen Formel I enthält, in der A einen gegebenenfalls substituierten zweiwertigen Rest bedeutet, der den Molekülteil -C=C- zu einem aromatischen oder heterocyclischen Ring vervollständigt, der Rest R1 wie auch der Rest R2 für ein Wasserstoffatom oder für einen Alkylrest mit 1 bis 4 Kohlenstoffatomen stehen und Me Chrom, Mangan, Eisen, Kobalt, Nickel, Kupfer oder Zink bedeutet. Von besonderer Bedeutung sind die Mangan-, Nickel- und insbesondere Kobaltkomplexe.According to a separate proposal, which does not belong to the state of the art, cathodes of fuel cells have an improved current-voltage behavior if the cathode and / or the catholyte are metal complexes of the general formula I contains, in which A is an optionally substituted divalent radical which completes the part of the molecule -C = C- to form an aromatic or heterocyclic ring, the radical R1 as well as the radical R2 represent a hydrogen atom or an alkyl radical having 1 to 4 carbon atoms and Me means chromium, manganese, iron, cobalt, nickel, copper or zinc. The manganese, nickel and especially cobalt complexes are of particular importance.
Vorliegende Erfindung betrifft Metallkomplexverbindungen der allgemeinen Formel in der X und Y gleiche oder verschiedene Bedeutung haben und für -H, -NH2, ~NOCH,, -OH, -Cl und CH, stehen und in der Me Eisen, Kobalt, Nickel, Mangan, Chrom oder Zink bedeutet.The present invention relates to metal complex compounds of the general formula in which X and Y have the same or different meanings and are -H, -NH2, ~ NOCH ,, -OH, -Cl and CH, and in which Me is iron, cobalt, nickel, manganese, chromium or zinc.
Die genannten Metallkomplexe können in einfacher Weise dadurch hergestellt werden, daß man 1,4-substituierte 2,5-Dicyananthrachinone mit den entsprechenden Metallsalzen oder auch den Metallen selbst bei erhöhten Temperaturen in einem Lösungsmittel für das Anthrachinon, z. B. Triäthylenglykol in Gegenwart eines Reduktionsmittels, z. B. Ammoniak, umsetzt. Die Umsetzung wird zweckmäßig bei Temperaturen von 150 bis 250°C durchgeführt.The metal complexes mentioned can be produced in a simple manner in this way be that one 1,4-substituted 2,5-dicyananthraquinones with the corresponding Metal salts or the metals themselves at elevated temperatures in a solvent for the anthraquinone, e.g. B. triethylene glycol in the presence of a reducing agent, z. B. ammonia, converts. The reaction is expediently carried out at temperatures of 150 carried out up to 250 ° C.
Die neuen Metallkomplexe eignen sich als Elektrokatalysatoren für Brennstoffzellen, vorzugsweise für die Kathodense#ite.The new metal complexes are suitable as electrocatalysts for Fuel cells, preferably for the cathode # ite.
Als Katalysatoren besonders geeignete Metallkomplexe sind solche mit Kobalt oder insbesondere Eisen als Zentralatom. Als Substituenten sind insbesondere die Amino- und die Hydroxylgruppen hervorzuheben.Metal complexes particularly suitable as catalysts are those with Cobalt or especially iron as the central atom. As substituents are in particular highlight the amino and hydroxyl groups.
Metallkomplexe enthaltende Kathoden bestehen in bekannter Weise aus einer porösen Gasdiffusionselektrode, in der der Sauerstoff in reiner Form oder aus der Luft aus der Gasphase elektrochemisch reduziert wird. Das Grundgerüst dieser porösen Elektrode muß elektronisch leitend sein. Es besteht z. B. aus Graphit, Titan, Tantal, Molybdän oder Wolfram, falls die Brennstoffzelle einen sauren Elektrolyten enthält. Für alkalische Elektrolyten sind außer den genannten Metallen z. B. auch Nickel, Eisen oder Kobalt sowie Chromnickelstähle brauchbar.Cathodes containing metal complexes are made in a known manner a porous gas diffusion electrode in which the oxygen is in pure form or is electrochemically reduced from the air from the gas phase. The basic structure of this porous electrode must be electronically conductive. There is z. B. made of graphite, titanium, Tantalum, Molybdenum or tungsten if the fuel cell contains an acidic electrolyte. For alkaline electrolytes, in addition to the metals mentioned, for. B. also nickel, Iron or cobalt as well as chromium-nickel steels can be used.
Die Einarbeitung des Metallkomplexes kann auf mehrere Arten erfolgen. Ist die inaktive, poröse Elektrode als Matrix vorgegeben, so läßt sich der Metallkomplex durch Tränken des porösen Systems mit einer Lösung oder Aufschlämmung des Metallkomplexes in ortanischen Lösungsmitteln, wie Pyridin oder N-Methylpyrrolidon, einbringen und durch nachfolgende Trocknung der Elektrode fixieren. Da die Metallkomplexe sich unzersetzt in 85 bis 97Xiger H2S04 lösen, kann auch eine solche Lösung zur Tränkung des porösen Systems dienen. Durch anschließende Auslaugung mit destilliertem Wasser fällt der Katalysator auf den Porenwandungen des porösen Systems aus. Da sich die Komplexe selbst bei Temperaturen oberhalb 3000C unzersetzt sublimieren lassen, besteht auch die Möglichkeit, durch Einsublimieren in die Poren eine Aktivierung zu erzielen.The incorporation of the metal complex can be done in several ways. If the inactive, porous electrode is given as a matrix, the metal complex can be by soaking the porous system with a solution or slurry of the metal complex in ortanic solvents, such as pyridine or N-methylpyrrolidone, and fix by subsequent drying of the electrode. Because the metal complexes Dissolve undecomposed in 85 to 97X H2S04, such a solution can also be used for impregnation serve the porous system. By subsequent leaching with distilled water the catalyst precipitates on the pore walls of the porous system. Since the Allow complexes to sublime without decomposition even at temperatures above 3000C also the possibility of achieving activation by subliming into the pores.
Das poröse Grundgerüst wird auf bekannte Weise aus den entsprechenden Pulvern durch Sintern, Kaltpressen, Warmpressen, Flamm- oder Plasmaspritzen hergestellt. Man kann die Pulver auch in Mischung mit einem Bindemittel, wie Polytetrafluoräthylen, Polyäthylen, Polypropylen, gegebenenfalls in Gegenwart eines Porenbildners, wie Na2S04 oder Polyvinylalkohol, der anschließend wieder herausgelöst wird, verpressen.The porous basic structure is made in a known manner from the corresponding Powders produced by sintering, cold pressing, hot pressing, flame or plasma spraying. The powder can also be mixed with a binder such as polytetrafluoroethylene, Polyethylene, polypropylene, optionally in the presence of a pore former, such as Press Na2S04 or polyvinyl alcohol, which is then dissolved out again.
Eine weitere Herstellungsmöglichkeit für die Katalysatorelektroden besteht z. B. darin, daß das zur Herstellung der porösen Elektrode vorgesehene elektronisch leitende Material zusammen mit dem fein verteilten Metallkomplex, gegebenenfalls unter Zusatz eines Bindemittels und eines Porenbildners, innig vermischt und zu einer porösen Elektrode weiterverarbeitet wird.Another manufacturing option for the catalyst electrodes consists z. B. is that provided for the production of the porous electrode electronically conductive material together with the finely divided metal complex, if appropriate with the addition of a binder and a pore former, intimately mixed and closed a porous electrode is processed further.
Dabei darf natürlich die Zersetzungstemperatur der Metallkomplexe nicht überschritten werden.Of course, the decomposition temperature of the metal complexes is allowed not be exceeded.
Die erwähnten Mischungen aus elektronisch leitendem Material und den Metallkomplexen können auch zur Herstellung von Schüttelektroden nach Grüneberg, gestützten Elektroden nach v. Sturm oder Dispersionselektroden nach Gerischer verwendet werden.The mentioned mixtures of electronically conductive material and the Metal complexes can also be used to make shaking electrodes after Grüneberg, supported electrodes according to v. Sturm or dispersion electrodes according to Gerischer be used.
Durch Zusatz von Acetogenruß oder anderen Kohlearten mit basischen Oberflächengruppen kann die katalytische Aktivitat der Metallkomplexe gesteigert werden.By adding acetogen black or other types of carbon with basic Surface groups can increase the catalytic activity of the metal complexes will.
Als Elektrolyte können prinzipiell in bekannter Weise sowohl saure als auch alkalische Flüssigkeiten eingesetzt werden, wobei lediglich darauf zu achten ist, daß der gewählte Elektrolyt die Metallkomplexe nicht zersetzt und die elektronisch leitende Matrix nicht angreift.In principle, both acidic electrolytes can be used as electrolytes in a known manner as well as alkaline liquids are used, whereby only care must be taken is that the chosen electrolyte does not decompose the metal complexes and those electronically does not attack the conductive matrix.
Der Kathode werden die Metallkomplexe der obengenannten allgemeinen Formel in Abhängigkeit von der Porosität und dem Material in Mengen von 0,1 bis 60 Ges., bezogen auf das Gewicht der metallisch leitenden Schicht der Kathode zugesetzt. Werden die Metallkomplexe ausschließlich auf die Oberfläche der Kathode, z. B. durch Imprägnieren aufgebracht, so genügen geringere Mengen, während man für den Fall, daß diese Verbindungen in der ganzen Elektrode verteilt sind, zweckmäßig größere Mengen verwendet. Es ist auch möglich, die Metallkomplexe anstelle sie in die Kathode einzuverleiben, auch dem Katholyten zuzusetzen.The metal complexes of the above-mentioned general are used for the cathode Formula depending on the porosity and the material in amounts from 0.1 to 60 total, based on the weight of the metallically conductive layer added to the cathode. If the metal complexes are only applied to the surface of the cathode, e.g. B. by Impregnation applied, then smaller amounts are sufficient, while for the case that these connections are distributed throughout the electrode, expediently larger ones Quantities used. It is also possible to place the metal complexes in the cathode incorporated, also added to the catholyte.
Im Katholyten wird die Konzentration der Komplexverbindung durch die Löslichkeit bestimmt, es sei denn, man verwendet eine Aufschlämmung. Selbstverständlich ist es auch möglich, die Metallkomplexe sowohl der Kathode als auch dem Katholyten zuzusetzen.In the catholyte, the concentration of the complex compound is determined by the Solubility determines unless a slurry is used. Of course it is also possible to use the metal complexes of both the cathode and the catholyte to add.
Die mit den neuen Metallkomplexen versehenen Elektroden können als Sauerstoffkathoden in Brennstoffzellen mit flüssigen, gasförmigen oder festen Brennstoffen sowie in Primär- und Sekundärbatterien, z. B. in der Zink-Luft-Batterie, eingesetzt werden.The electrodes provided with the new metal complexes can be used as Oxygen cathodes in fuel cells with liquid, gaseous or solid fuels as well as in primary and secondary batteries, e.g. B. in the zinc-air battery used will.
Sie können aber auch für Elektrolysezellen, in denen elektrochemische Oxidationen ablaufen, als Ersatz für die bekannten Wasserstoffkathoden eingesetzt werden, da sie die Zellspannung um etwa 1 V erniedrigen.But they can also be used for electrolytic cells in which electrochemical Oxidations run off, used as a replacement for the well-known hydrogen cathodes as they lower the cell voltage by about 1 V.
Die in den Beispielen genannten Teile bedellten Pichtsteile.The parts mentioned in the examples are covered with bonded parts.
Beispiel 1 Der Eisenkomplex des aminosubstituierten Anthrachinoncyanins wird wie folgt hergestellt: 11,6 Teile 1,4-Diamino-2,5-dicyanoanthrachinon werden in 150 Teilen Triäthylenglykol mit 2,06 Teilen FeS04x2H20 unter Durchleiten von Ammoniak auf 200 0C erhitzt. Nach ca. 2 bis 3 Stunden ist die Reaktion beendet; nach Abkühlung auf ca. 1000C wird abfiltriert, zuerst mit Triäthylenglykol, dann mit Wasser gewaschen und getrocknet. Example 1 The iron complex of amino-substituted anthraquinone cyanine is made as follows: 11.6 parts of 1,4-diamino-2,5-dicyanoanthraquinone are made in 150 parts of triethylene glycol with 2.06 parts of FeS04x2H20 while passing through Ammonia heated to 200 ° C. The reaction has ended after about 2 to 3 hours; after cooling to approx. 1000C it is filtered off, first with triethylene glycol, then washed with water and dried.
Ausbeute: 10,5 Teile Eisenkomplex.Yield: 10.5 parts of iron complex.
Eine durch diesen Komplex katalysierte Sauerstoff-Dispersionselektrode (vgl. H. Gerischer und J. Held, Ber. Bunsengesellsohaft physik. Chemie 67 (1963) 921), wird wie folgt hergestellt: 100 mg des Rohproduktes aus der Synthese werden in 100 g chemisch reiner 9-gew.iger Schwefelsäure gelöst. In der Lösung werden 100 mg unverdichteter Acetogenruß dispergiert. Die Dispersion erfolgt schnell und vollständig, da der Ruß basische Oberflächengruppen hat. Die frisch bereitete Mischung wird in 955 ml m mH2S04 unter Rühren eingetropft, die sich bereits im Meßgefäß befindet. Es entsteht eine Suspension von 100 mg Katalysator + 100 mg Acetogenruß in 1 1 4,5 n H2S04. Das zylindrische Meßgefäß aus Glas ist mit einem Gitterrührer (500 UpM), einem Gaseinleitungsrohr (1 1/min), einer Auffängerelektrode und einer Gegenelektrode (Pt, über Fritte abgetrennt) ausgestattet. Die Auffängerelektrode besteht aus einem rechteckigen Rahmen aus 1 mm-Golddraht, auf den ein Gold/Platin (90/10)-Netz mit 1000 Maschen pro cm2 aufgeschweißt ist. Die scheinbare Fläche des Netzes beträgt 4,5 cm2. Die Auffängerelektrode wird an der peripherie des Gefäßes so angeordnet, daß die dispergierten Teilchen möglichst senkrecht auf die Elektrode prallen. Das potential der Elektrode wird über eine Luggin-Kapillare gegen eine Hg/Hg2S04-Elektrode in 1 m H2S04 gemessen.An oxygen dispersion electrode catalyzed by this complex (cf. H. Gerischer and J. Held, Ber.Bunsengesellsohaft physik. Chemie 67 (1963) 921), is produced as follows: 100 mg of the crude product from the synthesis are used dissolved in 100 g of chemically pure 9% strength by weight sulfuric acid. The solution will be 100 mg of uncompacted acetogen black dispersed. The dispersion takes place quickly and completely, because the carbon black has basic surface groups. The freshly prepared mixture is in 955 ml of m mH2S04, which is already in the measuring vessel, were added dropwise with stirring. A suspension of 100 mg of catalyst + 100 mg of acetogen black in 1 1 4.5 is formed n H2S04. The cylindrical measuring vessel made of glass is equipped with a grid stirrer (500 rpm), a gas inlet pipe (1 1 / min), a collecting electrode and a counter electrode (Pt, separated by a frit) equipped. The collecting electrode consists of one Rectangular frame made of 1 mm gold wire on which a gold / platinum (90/10) mesh with 1000 meshes per cm2 is welded on. The apparent area of the network is 4.5 cm2. The collector electrode is placed on the periphery of the vessel so that that the dispersed particles hit the electrode as perpendicularly as possible. That The potential of the electrode is measured against an Hg / Hg2S04 electrode via a Luggin capillary measured in 1 m H2S04.
Die Messung der Stromspannungskurve erfolgt bei 25 0C mit Hilfe eines elektronischen Potentiostaten. Die Kurve wird in einem filr die Praxis interessanten Potentialbereich, nämlich UH = 1000 bis 600 mV, gemessen (UH - Potential gegen die Normalwasserstoffe#lektrode). Beginnend bei UH 1000 mV wiXd mit einer Spannungsgeschwindigkeit von 50 mV/min gemessen. 1/2 Stunde vor der Messung und während der Messung selbst wird Sauerstoff mit einer Geschwindigkeit von 1 1/min durch die Apparatur geleitet.The current-voltage curve is measured at 25 ° C. with the aid of a electronic potentiostats. The curve becomes interesting in practice Potential range, namely UH = 1000 to 600 mV, measured (UH - potential against the Normal hydrogen electrode). Starting at UH 1000 mV wiXd with a Tension speed measured at 50 mV / min. 1/2 hour before the measurement and during the measurement itself oxygen is passed through the apparatus at a rate of 1 1 / min.
In der Figur ist die auf diese Weise gemessene Stromspannungskurve als dickausgezogene Kurve wiedergegeben. Zum Vergleich sind zwei Kurven eingetragen, die unter denselben Bedingungen mit Dispersionselektroden mit der gleichen Menge an monomeren (punktierte Kurve) bzw. polymeren (strichlierte Kurve) Eisenphthalocyanin erhalten wurden. Das letztere ist als der aktivste Elektrokatalysator in der Phthalocyaninreihe bekannt. Die Kurven zeigen, daß bei U, 600 mV der neue Elektrokatalysator Ströme ergibt, die um einen Faktor 2bis 3 besser sind als bei den Fe-Phthalocyaninen.In the figure is the current-voltage curve measured in this way shown as a bold curve. Two curves have been entered for comparison, those under the same conditions with dispersive electrodes with the same amount to monomeric (dotted curve) or polymeric (dashed curve) iron phthalocyanine were obtained. The latter is considered to be the most active electrocatalyst in the phthalocyanine series known. The curves show that the new electrocatalyst has currents at U.600 mV results that are a factor of 2 to 3 better than the Fe phthalocyanines.
Der Strom ändert sich bei 50stündigem Dauerbetrieb bei diesem Arbeitspotential (unter kontinuierlichem Durchleiten von Sauerstoff) praktisch nicht. Im Falle der Eisenphthalocyanine beobachtet man nach dieser Zeit bereits eine merkliche Abnahme des Stromes.The current changes with 50 hours of continuous operation at this work potential (with continuous passage of oxygen) practically not. In case of After this time, iron phthalocyanines already show a noticeable decrease of the stream.
Beispiel 2 Der Eisenkomplex des hydroxylsubstituierten Anthrachinoncyanins wird wie folgt hergestellt: 10 Teile 1>4-Dihydroxy-2,3-dicyananthrachinon werden mit 1,78 Teilen FeSO4x2H20 in 125 Teilen Triäthylenglykol verrührt. Die Mischung wird unter Einleiten von Ammoniakgas 6 Stunden lang auf 200cm erhitzt. Anschließend läßt man auf ca. 1000C abkühlen, filtriert heiß, wäscht mit Methanol und Wasser und trocknet bei 800c im Vakuum. Man erhält 9,5 Teile des Eisenkomplexes. Example 2 The iron complex of hydroxyl-substituted anthraquinone cyanine is prepared as follows: 10 parts of 1> 4-dihydroxy-2,3-dicyananthraquinone become stirred with 1.78 parts of FeSO4x2H20 in 125 parts of triethylene glycol. The mixture is heated to 200 cm for 6 hours while passing in ammonia gas. Afterward allowed to cool to about 1000C, filtered hot, washed with methanol and water and dries at 800c in a vacuum. 9.5 parts of the iron complex are obtained.
Die entsprechenden Komplexe des Kobalts, Nickels, Mangans, Chroms und Zinks können auf analoge Weise hergestellt werden, indem man anstelle von Eisensulfat die entsprechenden Sulfate oder Chloride dieser Metalle einsetzt.The corresponding complexes of cobalt, nickel, manganese, chromium and zinc can be prepared in an analogous manner by using instead of iron sulfate the corresponding sulfates or chlorides of these metals are used.
Claims (1)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE2125590A DE2125590C3 (en) | 1971-05-24 | 1971-05-24 | ten anthraquinone cyanine |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE2125590A DE2125590C3 (en) | 1971-05-24 | 1971-05-24 | ten anthraquinone cyanine |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| DE2125590A1 true DE2125590A1 (en) | 1972-12-07 |
| DE2125590B2 DE2125590B2 (en) | 1980-06-04 |
| DE2125590C3 DE2125590C3 (en) | 1981-02-19 |
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ID=5808711
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DE2125590A Expired DE2125590C3 (en) | 1971-05-24 | 1971-05-24 | ten anthraquinone cyanine |
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| DE (1) | DE2125590C3 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2003083967A2 (en) * | 2002-03-27 | 2003-10-09 | Regenesys Technologies Limited | An electrode for the reduction of polysulfide species |
| EP2442389A1 (en) * | 2009-06-10 | 2012-04-18 | Japan Science And Technology Agency | Electrode catalyst for fuel cell and use thereof |
-
1971
- 1971-05-24 DE DE2125590A patent/DE2125590C3/en not_active Expired
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2003083967A2 (en) * | 2002-03-27 | 2003-10-09 | Regenesys Technologies Limited | An electrode for the reduction of polysulfide species |
| WO2003083967A3 (en) * | 2002-03-27 | 2004-10-28 | Regenesys Tech Ltd | An electrode for the reduction of polysulfide species |
| EP2442389A1 (en) * | 2009-06-10 | 2012-04-18 | Japan Science And Technology Agency | Electrode catalyst for fuel cell and use thereof |
| EP2442389A4 (en) * | 2009-06-10 | 2015-02-25 | Japan Science & Tech Agency | Electrode catalyst for fuel cell and use thereof |
| US10910654B2 (en) | 2009-06-10 | 2021-02-02 | Japan Science And Technology Agency | Electric power generation method using electrode catalyst for fuel cell |
Also Published As
| Publication number | Publication date |
|---|---|
| DE2125590C3 (en) | 1981-02-19 |
| DE2125590B2 (en) | 1980-06-04 |
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