NL8003898A - Colloidal oxidn. catalyst from ruthenium tetra:oxide - and inorganic carrier in water, esp. for solar energy storage cell - Google Patents
Colloidal oxidn. catalyst from ruthenium tetra:oxide - and inorganic carrier in water, esp. for solar energy storage cell Download PDFInfo
- Publication number
- NL8003898A NL8003898A NL8003898A NL8003898A NL8003898A NL 8003898 A NL8003898 A NL 8003898A NL 8003898 A NL8003898 A NL 8003898A NL 8003898 A NL8003898 A NL 8003898A NL 8003898 A NL8003898 A NL 8003898A
- Authority
- NL
- Netherlands
- Prior art keywords
- catalyst
- water
- colloidal
- process according
- copolymer
- Prior art date
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 46
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 31
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 title claims description 14
- 229910052707 ruthenium Inorganic materials 0.000 title claims description 11
- 238000004146 energy storage Methods 0.000 title claims description 6
- 210000000352 storage cell Anatomy 0.000 title claims description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 20
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 17
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims abstract description 15
- 238000000354 decomposition reaction Methods 0.000 claims abstract description 14
- 229910052751 metal Inorganic materials 0.000 claims abstract description 11
- 239000002184 metal Substances 0.000 claims abstract description 11
- 239000003381 stabilizer Substances 0.000 claims abstract description 9
- 229920001577 copolymer Polymers 0.000 claims abstract description 8
- 229920005606 polypropylene copolymer Polymers 0.000 claims abstract description 5
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(iv) oxide Chemical compound O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 claims description 28
- 238000000034 method Methods 0.000 claims description 20
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 14
- 239000001301 oxygen Substances 0.000 claims description 14
- 229910052760 oxygen Inorganic materials 0.000 claims description 14
- 238000007254 oxidation reaction Methods 0.000 claims description 9
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 8
- 239000001257 hydrogen Substances 0.000 claims description 8
- 229910052739 hydrogen Inorganic materials 0.000 claims description 8
- 239000004408 titanium dioxide Substances 0.000 claims description 8
- 150000001728 carbonyl compounds Chemical class 0.000 claims description 7
- 238000002360 preparation method Methods 0.000 claims description 7
- 239000000084 colloidal system Substances 0.000 claims description 4
- -1 platinum series metals Chemical class 0.000 claims description 3
- 239000007864 aqueous solution Substances 0.000 claims description 2
- 150000003057 platinum Chemical class 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 abstract description 8
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 abstract description 6
- 239000007789 gas Substances 0.000 abstract description 4
- 239000000843 powder Substances 0.000 abstract description 4
- 239000004065 semiconductor Substances 0.000 abstract description 3
- 230000003197 catalytic effect Effects 0.000 abstract description 2
- 238000002485 combustion reaction Methods 0.000 abstract description 2
- 150000004676 glycans Chemical class 0.000 abstract description 2
- 239000000543 intermediate Substances 0.000 abstract description 2
- 229910000510 noble metal Inorganic materials 0.000 abstract description 2
- 229920001282 polysaccharide Polymers 0.000 abstract description 2
- 239000005017 polysaccharide Substances 0.000 abstract description 2
- 229920000036 polyvinylpyrrolidone Polymers 0.000 abstract description 2
- 239000001267 polyvinylpyrrolidone Substances 0.000 abstract description 2
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 abstract description 2
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 abstract 2
- 229910002370 SrTiO3 Inorganic materials 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 13
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 7
- 230000003647 oxidation Effects 0.000 description 5
- ROFVEXUMMXZLPA-UHFFFAOYSA-N Bipyridyl Chemical compound N1=CC=CC=C1C1=CC=CC=N1 ROFVEXUMMXZLPA-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 239000007983 Tris buffer Substances 0.000 description 2
- 210000004027 cell Anatomy 0.000 description 2
- 230000001419 dependent effect Effects 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 229910052741 iridium Inorganic materials 0.000 description 2
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229910052703 rhodium Inorganic materials 0.000 description 2
- 239000010948 rhodium Substances 0.000 description 2
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- 239000008351 acetate buffer Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000004530 micro-emulsion Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229910052762 osmium Inorganic materials 0.000 description 1
- SYQBFIAQOQZEGI-UHFFFAOYSA-N osmium atom Chemical compound [Os] SYQBFIAQOQZEGI-UHFFFAOYSA-N 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229910003446 platinum oxide Inorganic materials 0.000 description 1
- 229920002401 polyacrylamide Polymers 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920001184 polypeptide Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 1
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 description 1
- 229910052939 potassium sulfate Inorganic materials 0.000 description 1
- 235000011151 potassium sulphates Nutrition 0.000 description 1
- 102000004196 processed proteins & peptides Human genes 0.000 description 1
- 108090000765 processed proteins & peptides Proteins 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- YAYGSLOSTXKUBW-UHFFFAOYSA-N ruthenium(2+) Chemical compound [Ru+2] YAYGSLOSTXKUBW-UHFFFAOYSA-N 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000009738 saturating Methods 0.000 description 1
- 238000001429 visible spectrum Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/20—Carbonyls
-
- 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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
- B01J31/068—Polyalkylene glycols
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
- B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
- B01J31/181—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine
- B01J31/1815—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine with more than one complexing nitrogen atom, e.g. bipyridyl, 2-aminopyridine
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J33/00—Protection of catalysts, e.g. by coating
-
- 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
- B01J35/20—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state
- B01J35/23—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state in a colloidal state
-
- 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
- B01J35/39—Photocatalytic properties
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/04—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of inorganic compounds, e.g. ammonia
- C01B3/042—Decomposition of water
-
- 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
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/70—Oxidation reactions, e.g. epoxidation, (di)hydroxylation, dehydrogenation and analogues
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/02—Compositional aspects of complexes used, e.g. polynuclearity
- B01J2531/0202—Polynuclearity
- B01J2531/0211—Metal clusters, i.e. complexes comprising 3 to about 1000 metal atoms with metal-metal bonds to provide one or more all-metal (M)n rings, e.g. Rh4(CO)12
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/82—Metals of the platinum group
- B01J2531/822—Rhodium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/82—Metals of the platinum group
- B01J2531/825—Osmium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/82—Metals of the platinum group
- B01J2531/827—Iridium
-
- 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
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
- Y02P20/133—Renewable energy sources, e.g. sunlight
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Combustion & Propulsion (AREA)
- Catalysts (AREA)
Abstract
Description
'· / > K.0. 29251K.0. 29251
Werkwijze voor de bereiding van colloidale rutheniumdioxidekataly-satoren, werkwijze voor de ontleding van water onder toepassing van een dergelijke katalysator, alsmede oei voor de opslag van zonne-energie, die water en een dergelijke katalysator bevat.Process for the preparation of colloidal ruthenium dioxide catalysts, process for the decomposition of water using such a catalyst, and solar energy storage containing water and such a catalyst.
De uitvinding heeft betrekking op een werkwijze voor de bereiding van colloidale rutheniumdioxide-katalysatoren voor oxidatie-reacties, in het bijzonder voor de ontleding van water.The invention relates to a process for the preparation of colloidal ruthenium dioxide catalysts for oxidation reactions, in particular for the decomposition of water.
De fotochemische ontleding van water in waterstof en zuurstof 5 onder invloed van licht in het zichtbare spectrum is een belangrijke werkwijze, in het bijzonder met betrekking tot de opslag van zonne-energie. (Science, 189. blz. 852-871 (1975); Accts. Chem. Ees. JM_, blz. 569-377 (1978) en Science, 202, blz. 705-712 (1978)). Deze reactie, waarbij de reductie van water tot waterstof is gekoppeld aan 10 de oxidatie van water tot zuurstof, is recentelijk uitgevoerd in een systeem, dat microheterogene metaalkatalysatoren bevat, waarbij colloidaal platina en rutheniumdioxide worden vermeld met betrekking tot de gelijktijdige ontwikkeling van waterstof en zuurstof. (Angew. Chemie, £1_, (1979)> hlz. 759-760). Eouv. J. Chim. 2, blz.The photochemical decomposition of water into hydrogen and oxygen under the influence of light in the visible spectrum is an important method, particularly with regard to the storage of solar energy. (Science, 189, pp. 852-871 (1975); Accts. Chem. Ees. JM_, pp. 569-377 (1978) and Science, 202, pp. 705-712 (1978)). This reaction, in which the reduction of water to hydrogen is coupled to the oxidation of water to oxygen, has recently been carried out in a system containing microheterogenic metal catalysts reporting colloidal platinum and ruthenium dioxide with respect to the simultaneous development of hydrogen and oxygen . (Angew. Chemie, £ 1 (1979)> 757-760). Eouv. J. Chim. 2, p.
15 423-426, Er. 7 —1979 > vermeldt dat de snelheid van de vorming van zuurstof sterk afhankelijk is van de toestand, de hoeveelheid van het ruthenium^dioxide en de pH; naast rutheniumdioxide kunnen bijvoorbeeld als katalysator oxides van mangaan, platina, ruthenium, rodium en iridium op een aluminiumoxide-drager worden toegepast.15 423-426, Er. 7-1979> mentions that the rate of oxygen formation is highly dependent on the state, the amount of the ruthenium dioxide and the pH; in addition to ruthenium dioxide, for example, as a catalyst, oxides of manganese, platinum, ruthenium, rhodium and iridium on an aluminum oxide support can be used.
20 De bereiding van actieve katalysatoren met een groot oppervlak en een langdurige stabiliteit is van beslissende betekenis voor het succes van de reactie. Vooral de stabiliteitsduur is bij de tot dusverre bekende colloidale katalysatorsystemen zeer kort, in de orde van enkele uren.The preparation of large surface area active catalysts of long term stability is critical to the success of the reaction. In particular, the stability time in the hitherto known colloidal catalyst systems is very short, on the order of several hours.
25 De onderhavige uitvinding beoogt vooral aan dit laatste nadeel tegemoet te komen. Gevonden werd een werkwijze van het in de aanhef genoemde type, waarbij colloidale rutheniumdioxide-katalysatoren . worden verkregen, die gedurende verscheidene maanden de colloidale vorm behouden en daarbij niet de katalytische activiteit verliezen.The present invention particularly aims to obviate this last drawback. A process of the type mentioned in the preamble, involving colloidal ruthenium dioxide catalysts, was found. which retain the colloidal form for several months without losing the catalytic activity.
30 De uitvinding is gekenmerkt, doordat men stabiele colloidale katalysatoren bereidt door rutheniumtetraoxide in water te laten inwerken op een anorganische drager.The invention is characterized in that stable colloidal catalysts are prepared by allowing ruthenium tetraoxide in water to act on an inorganic support.
Als anorganische drager worden titaandioxide en andere oxidi- sche halfgeleiders, zoals SrTiO,, in poedervorm, die aan een redu- 5 8003898 ,- 'v - 2 - cerende "behandeling zijn onderworpen, gebruikt. Ook kannen poeders van edelmetalen, "bijvoorbeeld Pt en Au, en metaalcarbonylverbindingen van metalen uit de platina-reeks worden gebruikt als drager, bij voorkeur Os^CO^, Ir^C0^2 en RhgCO^g.As an inorganic carrier, titanium dioxide and other oxidic semiconductors, such as powdered SrTiO4, which have been subjected to a reducing "treatment, are also used. Noble metal powders, for example, Pt. and Au, and platinum series metal carbonyl compounds of metals are used as the support, preferably Os ^ CO ^, Ir ^ CO ^ 2 and RhgCO ^ g.
5 Bij de werkwijze volgens de uitvinding worden de bovengenoem de dragers tijdens de inwerking van rutheniumtetraoxide in water bedekt met een laagje rutheniumdioxide. Bij de omzetting van rutheniumtetraoxide in rutheniumdioxide is geen katalysator nodig. Hierbij wordt opgemerkt, dat niet-gereduceerd titaandioxide en de ande-10 re bovengenoemde oxidische halfgeleiders niet leiden tot de vorming van colloidale oplossingen.In the process according to the invention, the carriers mentioned above are covered with a layer of ruthenium dioxide during the action of ruthenium tetraoxide in water. No catalyst is required in the conversion of ruthenium tetraoxide to ruthenium dioxide. It should be noted that non-reduced titanium dioxide and the other oxidic semiconductors mentioned above do not lead to the formation of colloidal solutions.
Be uitvinding heeft tevens betrekking op een werkwijze voor het ontleden van water, waarbij de ontleding wordt uitgevoerd bij aanwezigheid van een volgens bovengenoemde werkwijze verkregen col-15 loid katalysatorsysteem. Tevens heeft de uitvinding betrekking op een cel voor de opslag van zonneënergie, waarin water wordt ontleed in Hg en 0g met behulp van de volgens de uitvinding verkregen kata-lysatorsystemen (Angew. Chem. £1_, blz. 759-760 (1979))·The invention also relates to a process for decomposing water, wherein the decomposition is carried out in the presence of a colloid catalyst system obtained according to the above process. The invention also relates to a solar energy storage cell in which water is decomposed into Hg and 0g using the catalyst systems obtained according to the invention (Angew. Chem. £ 1, pp. 759-760 (1979)). ·
Bij voorkeur wordt aan het katalysatorsysteem een stabiliseer-20 middel toegevoegd. Be volgens de uitvinding verkregen gestabiliseerde colloidale katalysatoren zijn actieve katalysatoren voor de oxidatie van water tot zuurstof (onderstaande vergelijking 3)·A stabilizing agent is preferably added to the catalyst system. The stabilized colloidal catalysts obtained according to the invention are active catalysts for the oxidation of water to oxygen (equation 3 below)
Als stabiliseermiddel worden bij de ontleding van water in water oplosbare homo- of copolymeren met een molecuulgewicht van 25 5*000 - 100.000 gebruikt. Voorbeelden van dergelijke polymeren zijn polyethyleenglycol, propyleenglycol-ethyleenglycol-copolymeer, poly-styreen-maleïnezuuranhydride, polyvinylpyrrolidon, polyvinylalco-hol, polyacrylamide, polyacrylzuur-zouten, polysacchariden en poly-peptiden. Bij voorkeur wordt een copolymeer van propyleenglycol en 30 ethyleenglycol gebruikt. Het stabiliseermiddel met de meeste voorkeur is een 0,5 gew.% oplossing in water van een 70:30 copolymeer van propyleenglycol en ethyleenglycol met een molecuulgewicht van 20.000.As a stabilizing agent, water-soluble homo- or copolymers with a molecular weight of 5 * 000-100,000 are used in the decomposition of water. Examples of such polymers are polyethylene glycol, propylene glycol-ethylene glycol copolymer, polystyrene-maleic anhydride, polyvinylpyrrolidone, polyvinyl alcohol, polyacrylamide, polyacrylic acid salts, polysaccharides and polypeptides. Preferably, a copolymer of propylene glycol and ethylene glycol is used. The most preferred stabilizer is a 0.5 wt% aqueous solution of a 70:30 copolymer of propylene glycol and ethylene glycol having a molecular weight of 20,000.
Een cel voor de opslag van zonneënergie is gebaseerd op het 35 volgende reactieschema: 4 Ba (ll)Mpy32+ 4 /Sa (II) Mp72*J * (1) 8003898 4 /"Ru(ll)Mpy32+_7S+ MV-2+ -* 4 Hu(lll)bipy53+ + 4M7+ (2) - 3 - 4 Ru(lll)bipy33+ + 2 HgO C0^Q^daal>Ra(lI)bipy52+ + 4H+ + 0£ (?) 4 M7+ + 4 H20 °Qp^q-aal> 4 M72+ + 2H2 + 4 OH" (4)A solar energy storage cell is based on the following reaction scheme: 4 Ba (ll) Mpy32 + 4 / Sa (II) Mp72 * J * (1) 8003898 4 / "Ru (ll) Mpy32 + _7S + MV-2 + - * 4 Hu (lll) bipy53 + + 4M7 + (2) - 3 - 4 Ru (lll) bipy33 + + 2 HgO C0 ^ Q ^ daal> Ra (lI) bipy52 + + 4H + + 0 £ (?) 4 M7 + + 4 H20 ° Qp ^ q-eal> 4 M72 + + 2H2 + 4 OH "(4)
Ru(ll)bipy32+ = ruthenium(II)trisbipyridine-ion (negatief ion is 5 01")* MV = methylviologeenion (N, N1-dimethyl-4,41-bipyridine- diohloride) lis lichtabsorberende kleurstof wordt bijvoorbeeld het ruthe-nium(ll)trisbipyridinièhloride in combinatie met andere componenten, 10 zoals het methylviologeen, gebruikt.Ru (ll) bipy32 + = ruthenium (II) tris bipyridine ion (negative ion is 5 01 ") * MV = methylviologene ion (N, N1-dimethyl-4,41-bipyridine diohloride) lis light absorbing dye, for example, the ruthenium ( ll) tris bipyridinium chloride used in combination with other components, such as the methyl viologene.
He snelheid van de vorming van zuurstof is afhankelijk van de pH en optimaal bij pH = 3,5.The rate of oxygen formation is dependent on the pH and optimal at pH = 3.5.
He lage kosten van Ti02, de gemakkelijke bereiding, de activiteit en de langdurige stabiliteit van deze katalysatoren zijn opmer-15 kelijk. Toepassing in andere systemen, waarin de oxidatie van water tot zuurstof is gekoppeld aan de reductie ervan tot waterstof in een microemulsie (j.Am. Chem. Soc. 102 (1980) biz. 246I-2462) of in een uit twee compartimenten bestaande cel met een membraan (Nature, 265 (1979) blz. 229-231) kan leiden tot de constructie van verbeter-20 de inrichtingen voor het opslaan van zonneënergie in de vorm van de brandstof waterstof. Ook kan de aldus gekatalyseerde ontleding van water worden gekoppeld aan de reductie van bijvoorbeeld kooldioxyde’ . tot methanol of tussenprodukten.The low cost of TiO2, the ease of preparation, the activity and the long-term stability of these catalysts are remarkable. Use in other systems, in which the oxidation of water to oxygen is linked to its reduction to hydrogen in a microemulsion (j. Am. Chem. Soc. 102 (1980) biz. 246I-2462) or in a two compartment cell with a membrane (Nature, 265 (1979) pp. 229-231) can lead to the construction of improved solar energy storage devices in the form of the fuel hydrogen. The thus catalyzed decomposition of water can also be linked to the reduction of, for example, carbon dioxide. to methanol or intermediates.
Hoewel de toepassing van de onderhavige katalysatoren in deze 25 aanvrage is beschreven met betrekking tot de ontleding van water in zonneënergiecellen, kunnen de katalysatoren ook voor andere oxida-tiereacties worden toegepast; bijvoorbeeld zijn zij in vaste vorm geschikt voor het oxideren van uitlaatgassen van verbrandingsmotoren.Although the application of the present catalysts has been described in this application with respect to the decomposition of water in solar energy cells, the catalysts may also be used for other oxidation reactions; for example, they in solid form are suitable for oxidizing exhaust gases from internal combustion engines.
30 He uitvinding wordt nader toegelicht aan de hand van de volgen de voorbeelden.The invention is further elucidated by means of the following examples.
Voorbeeld IExample I
Bereiding van de katalysator op basis van titaandioxide.Preparation of the catalyst based on titanium dioxide.
4 g titaandioxidepoeder, dat tevoren was gereduceerd bij 800°C 35 in een atmosfeer van stikstof en waterstof met een verhouding 3s1 gedurende 3 uren, werden geroerd in 125 nil water, waaraan 200 mg vast rutheniumtetraoxide werden toegevoegd. Het verkregen mengsel 8003898 V* -4-.4 g of titanium dioxide powder, which had previously been reduced at 800 ° C in an atmosphere of nitrogen and hydrogen in a ratio 3s1 for 3 hours, were stirred in 125 nil of water, to which 200 mg of solid ruthenium tetraoxide were added. The resulting mixture 8003898 V * -4-.
werd 20 uren geroerd bij omgevingstemperatuur. Een zwarte colloida-le oplossing van 5 gev.% rutheniumdioxide op titaandioxide werd verkregen na filtreren van niet-omgezet materiaal door een trechter met filtreerpapier.was stirred at ambient temperature for 20 hours. A black colloidal solution of 5% by weight ruthenium dioxide on titanium dioxide was obtained after filtering unreacted material through a funnel with filter paper.
5 Een monster van 35 ml van dit colloid werd onder roeren ver dund met 250 ml van een 0,5 gew.% oplossing van een 70:30 propyleen-glycol-ethyleenglycol-copolymeer (molecuulgewicht 20.000) in water, waarbij een microheterogene grijze oplossing werd verkregen.A 35 ml sample of this colloid was diluted with 250 ml of a 0.5 wt% solution of a 70:30 propylene-glycol-ethylene glycol copolymer (molecular weight 20,000) in water, with stirring, using a microheterogenic gray solution was obtained.
Deze oplossingen zijn actieve katalysatoren in de reactie, be-10 schreven in voorbeeld III, en blijven colloidaal en katalytisch actief gedurende meer dan 4 maanden.These solutions are active catalysts in the reaction described in Example III and remain colloidal and catalytically active for more than 4 months.
Voorbeeld IIExample II
Bereiding van de katalysator op basis van de metaalcarbonylverbin-dingen Os^CO^, Ir^CO.^ of EhgCO^.Preparation of the catalyst on the basis of the metal carbonyl compounds Os ^ CO ^, Ir ^ CO. ^ Or EhgCO ^.
15 150 mg van één van deze verbindingen werden gebracht in 5 ml water, dat 10 mg rutheniumtetraoxide bevatte. Dit mengsel liet men bij omgevingstemperatuur 20 uren staan onder af en toe schudden. Zwarte colloidale oplossingen werden verkregen na filtreren door een trechter met filtreerpapier. De katalysatoren behielden de col-20 loidale vorm gedurende 6-14 dagen, waarbij bleek, dat osmium stabieler was dan iridium, dat weer stabieler was dan rodium. De col-loiden kunnen worden gestabiliseerd door roeren met een 20 maal zo groot volume van een 0,5 gew.% oplossing van een 70:30 propyleen-glycol-ethyleenglycol-copolymeer (molecuulgewicht 20.000) in water. 25 Deze oplossingen zijn actieve katalysatoren in de reactie, be schreven in voorbeeld IV, en blijven colloidaal en katalytisch actief gedurende meer dan 4 maanden.150 mg of one of these compounds was placed in 5 ml of water containing 10 mg of ruthenium tetraoxide. This mixture was allowed to stand at ambient temperature for 20 hours with occasional shaking. Black colloidal solutions were obtained after filtering through a funnel with filter paper. The catalysts retained the colloidal form for 6-14 days, showing that osmium was more stable than iridium, which was again more stable than rhodium. The colloids can be stabilized by stirring with a 20-fold volume of a 0.5 wt% solution of a 70:30 propylene-glycol-ethylene glycol copolymer (molecular weight 20,000) in water. These solutions are active catalysts in the reaction described in Example IV and remain colloidal and catalytically active for more than 4 months.
De in de onderstaande voorbeelden genoemde oxidatiereactie verloopt aldus: 30 2 Ru(ll)bipy52+ + S2082" 2 Ra(lll)bipy55+ + 2S042“The oxidation reaction mentioned in the examples below proceeds as follows: 30 2 Ru (ll) bipy52 + + S2082 "2 Ra (lll) bipy55 + + 2S042"
4 Ru(lll)bipy53+ + 2H20 cö'ifoid^ 4 Ru(n)Mpy^ + 0£ + 4H+ Voorbeeld III4 Ru (lll) bipy53 + + 2H20 coifoid ^ 4 Ru (n) Mpy ^ + 0 £ + 4H + Example III
Oxidatie van water met katalysator, bereid volgens voorbeeld I.Oxidation of water with catalyst prepared according to example I.
33 ml van een oplossing van ruthenium(ll)trisbipyridine-dichlo-35 ride (10-½) en kal iump er sulfaat (Z2S20g) (10-2M), gebufferd op pH = 3j5> werd bestraald met een 250 W projectielamp (Osram Sylvaner), nadat met titaandioxide volgens voorbeeld I gestabiliseerd colloidaal rutheniumdioxide (5-20 mg Ru per liter) was toege- 8003898 - 5 - voegd. Ben krachtige ontwikkeling van zuurstof (1,7 ml in 10-20 minuten) -had plaats (0,078 mmol, 26 mmol per mmol Ru(ll)bipyjClg), waarbij de opbrengst aan zuurstof werd beperkt door de ontleding van Ru(ll)bipy^Cl2 tijdens het verloop van de reactie. Wanneer het 5 Su(ll)bipy^Cl2 ontleed raakt, kan vers Ru(ll)bipyjClg worden toegevoegd, waardoor de ontwikkeling van zuurstof opnieuw begint. Yoorbeeld 1733 ml of a solution of ruthenium (ll) trisbipyridine-dichlo-35 ride (10-½) and potassium sulfate (Z2S20g) (10-2M), buffered at pH = 3j5> was irradiated with a 250 W projection lamp (Osram Sylvaner), after colloidal ruthenium dioxide stabilized with titanium dioxide according to Example I (5-20 mg Ru per liter) was added 8003898-5. A vigorous development of oxygen (1.7 ml in 10-20 minutes) - took place (0.078 mmol, 26 mmol per mmol Ru (ll) bipyCl3), the oxygen yield being limited by the decomposition of Ru (ll) bipy ^ Cl2 during the course of the reaction. When the 5 Su (11) bipyCl 2 decomposes, fresh Ru (11) bipyCl 2 can be added, thereby restarting oxygen generation. Yoorbeeld 17
Oxidatie van water met katalysator bereid volgens voorbeeld II.Oxidation of water with catalyst prepared according to Example II.
33 ml van een oplossing van ruthenium(ll)trispyridine-dichlo-10 ride (10-½) en kaliumpersulfaat (KgSgOg) (10-2M),. met een acetaat-buffer gebufferd op pH = 3>5> werd bestraald met een 250 W projec-tielamp (Osram Sylvaner), nadat met een metaalcarbonylverbinding (volgens voorbeeld II) gestabiliseerd rutheniumdioxide (5-20 mg Ru per liter) was toegevoegd. Een krachtige ontwikkeling van zuur-15 stof (1,8 ml) had plaats bij omgevingstemperatuur in verloop van 20-50 minuten. Ra deze periode is het Ru(ll)bipyjClg ontleed. Na toevoeging van vers R^IlJbipy^Clg begon de ontwikkeling van zuurstof opnieuw.33 ml of a solution of ruthenium (11) trispyridine-dichlo-10 ride (10-½) and potassium persulfate (KgSgOg) (10-2M). buffered with an acetate buffer at pH = 3> 5> was irradiated with a 250 W projection lamp (Osram Sylvaner) after ruthenium dioxide (5-20 mg Ru per liter) stabilized with a metal carbonyl compound (according to example II) was added. A vigorous development of oxygen (1.8 ml) took place at ambient temperature in the course of 20-50 minutes. During this period the Ru (ll) bipyjClg has been dissected. After the addition of fresh R 1 / 4Bipy 2 Clg, oxygen generation started again.
Yoorbeeld 7 20 Potochemische ontleding van water in waterstof en zuurstof.Example 7 20 Potochemical decomposition of water into hydrogen and oxygen.
33 ml van een oplossing van Ru(ll)bipyjClg (5 x 10-½), MY2+ (methylviologeen) (10-½)) colloidaal Pt (100 mg Pt per liter) en colloidaal RuOg (30 mg Ru per liter) met een pH van 3>1» werd verzadigd met Ng (tot geen 0g meer aanwezig was) en bestraald met een 25 25Ο W projectielamp (Osram Sylvaner) bij 22,5°C. Na 60 minuten was 0,12 ml 0g aanwezig in de oplossing en Hg was aangetoond in de gasfase. Na opnieuw verzadigen met Ng werd de oplossing opnieuw bestraald, waarbij 0,22 ml 0g in 50 minuten verkregen werden. In een derde cyclus werd 0,08 ml 0g_geproduceerd (in totaal 0,019 mmol, 30 2,8 mmol met 0g per mmol Ru(ll)bipy^Clg), terwijl Hg in de gasfase aanwezig was. De reactiesnelheid was aanzienlijk gedaald. Na toevoeging van Ru(ll)bipy^Clg ( 5 x 10-½) begon de ontwikkeling van Hg en 0g opnieuw met een lagere snelheid.33 ml of a solution of Ru (ll) bipyjClg (5 x 10-½), MY2 + (methylviologene) (10-½)) colloidal Pt (100 mg Pt per liter) and colloidal RuOg (30 mg Ru per liter) with a pH of 3> 1 »was saturated with Ng (until no more 0g was present) and irradiated with a 25ΟW projection lamp (Osram Sylvaner) at 22.5 ° C. After 60 minutes, 0.12 ml of 0g was present in the solution and Hg was detected in the gas phase. After re-saturating with Ng, the solution was irradiated again, yielding 0.22 ml of 0g in 50 minutes. In a third cycle, 0.08 ml of 0g was produced (total 0.019mmol, 2.8mmol with 0g per mmole Ru (11) bipy ^ Clg), while Hg was present in the gas phase. The reaction speed had dropped considerably. After adding Ru (11) bipy ^ Clg (5 x 10-½), the development of Hg and 0g started again at a slower rate.
80038988003898
Claims (14)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| NL8003898A NL8003898A (en) | 1980-07-04 | 1980-07-04 | Colloidal oxidn. catalyst from ruthenium tetra:oxide - and inorganic carrier in water, esp. for solar energy storage cell |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| NL8003898A NL8003898A (en) | 1980-07-04 | 1980-07-04 | Colloidal oxidn. catalyst from ruthenium tetra:oxide - and inorganic carrier in water, esp. for solar energy storage cell |
| NL8003898 | 1980-07-04 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| NL8003898A true NL8003898A (en) | 1982-02-01 |
Family
ID=19835572
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| NL8003898A NL8003898A (en) | 1980-07-04 | 1980-07-04 | Colloidal oxidn. catalyst from ruthenium tetra:oxide - and inorganic carrier in water, esp. for solar energy storage cell |
Country Status (1)
| Country | Link |
|---|---|
| NL (1) | NL8003898A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108778503A (en) * | 2016-03-31 | 2018-11-09 | 日本瑞翁株式会社 | The manufacturing method of the dispersion liquid of particle containing metal and the manufacturing method of hydrogenating conjugated diene polymers |
-
1980
- 1980-07-04 NL NL8003898A patent/NL8003898A/en not_active Application Discontinuation
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108778503A (en) * | 2016-03-31 | 2018-11-09 | 日本瑞翁株式会社 | The manufacturing method of the dispersion liquid of particle containing metal and the manufacturing method of hydrogenating conjugated diene polymers |
| EP3437737A4 (en) * | 2016-03-31 | 2019-12-04 | Zeon Corporation | Method for preparing dispersion of metal-containing particles and method for producing hydrogenated conjugated diene polymer |
| US11266978B2 (en) | 2016-03-31 | 2022-03-08 | Zeon Corporation | Method for preparing dispersion of metal-containing particles and method for producing hydrogenated conjugated diene polymer |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Goss et al. | Spectral, electrochemical and electrocatalytic properties of 1, 10-phenanthroline-5, 6-dione complexes of transition metals | |
| Hurrell et al. | Electrocatalytic activity of electropolymerized films of bis (vinylterpyridine) cobalt (2+) for the reduction of carbon dioxide and oxygen | |
| US4382846A (en) | Simultaneous production of hydrogen and oxygen from water | |
| US9790605B2 (en) | Iridium complexes for electrocatalysis | |
| Hintermair et al. | Particle formation during oxidation catalysis with Cp* iridium complexes | |
| US4421617A (en) | Photolytic production of hydrogen from water | |
| Amouyal et al. | Photochemical production of hydrogen from water | |
| CN108298499B (en) | Method for decomposing and releasing hydrogen by catalyzing formic acid with water-soluble metal complex | |
| Greenbaum | Interfacial photoreactions at the photosynthetic membrane interface: an upper limit for the number of platinum atoms required to form a hydrogen-evolving platinum metal catalyst | |
| Narayanan et al. | Reduction of metal carbonyls via electron transfer. Formation and chain decomposition of formylmetal intermediates | |
| EP0070712A2 (en) | Catalysts for photo-assisted oxidation-reduction reactions | |
| Yamada et al. | Photocatalytic hydrogen evolution from carbon-neutral oxalate with 2-phenyl-4-(1-naphthyl) quinolinium ion and metal nanoparticles | |
| Mase et al. | Catalytic reduction of proton, oxygen and carbon dioxide with cobalt macrocyclic complexes | |
| Oishi | A water-soluble Wilkinson's complex as homogeneous catalyst for the photochemical reduction of water | |
| Wang et al. | New platinum and ruthenium Schiff base complexes for water splitting reactions | |
| Kelson et al. | Kinetic study of 2‐propanol and benzyl alcohol oxidation by alkaline hexacyanoferrate (III) catalyzed by a terpyridyl ruthenium complex | |
| Kaneko et al. | Photoinduced electron transfer from polystyrene pendant tris (2, 2′‐bipyridyl) ruthenium (II) complex to methylviologen | |
| NL8003898A (en) | Colloidal oxidn. catalyst from ruthenium tetra:oxide - and inorganic carrier in water, esp. for solar energy storage cell | |
| Jiang et al. | N-heterocyclic carbene-ligated metal complexes and clusters for photocatalytic CO 2 reduction | |
| WO2004049477A2 (en) | Metal alloy for electrochemical oxidation reactions and method of production thereof | |
| CN116212964B (en) | Iridium catalyst for hydrogen production from formic acid, and preparation method and application thereof | |
| JP4302819B2 (en) | Photochemical catalyst, photochemical decomposition method, and fuel cell | |
| Kiwi | Photochemical generation of reduced β-nicotinamide-adenine dinucleotide (induced by visible light) | |
| KR20240014053A (en) | Electrochemical reduction of carbon dioxide catalyzed by polyoxometalate | |
| JPH0235037B2 (en) |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A1B | A search report has been drawn up | ||
| BV | The patent application has lapsed |