US3917525A - Electrode for electrochemical reactions - Google Patents
Electrode for electrochemical reactions Download PDFInfo
- Publication number
- US3917525A US3917525A US486051A US48605174A US3917525A US 3917525 A US3917525 A US 3917525A US 486051 A US486051 A US 486051A US 48605174 A US48605174 A US 48605174A US 3917525 A US3917525 A US 3917525A
- Authority
- US
- United States
- Prior art keywords
- electrode
- rare earth
- atomic number
- perovskite structure
- cobaltite
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
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- 238000003487 electrochemical reaction Methods 0.000 title abstract description 5
- 229910052761 rare earth metal Inorganic materials 0.000 claims abstract description 28
- 150000002910 rare earth metals Chemical class 0.000 claims abstract description 28
- 229910052751 metal Inorganic materials 0.000 claims abstract description 23
- 239000002184 metal Substances 0.000 claims abstract description 21
- 229910052963 cobaltite Inorganic materials 0.000 claims abstract description 19
- 239000000758 substrate Substances 0.000 claims abstract description 12
- 150000001875 compounds Chemical class 0.000 claims description 33
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 10
- 229910052719 titanium Inorganic materials 0.000 claims description 10
- 239000010936 titanium Substances 0.000 claims description 10
- 229910052771 Terbium Inorganic materials 0.000 claims description 8
- GZCRRIHWUXGPOV-UHFFFAOYSA-N terbium atom Chemical compound [Tb] GZCRRIHWUXGPOV-UHFFFAOYSA-N 0.000 claims description 7
- 229910052688 Gadolinium Inorganic materials 0.000 claims description 6
- UIWYJDYFSGRHKR-UHFFFAOYSA-N gadolinium atom Chemical compound [Gd] UIWYJDYFSGRHKR-UHFFFAOYSA-N 0.000 claims description 6
- 229910052692 Dysprosium Inorganic materials 0.000 claims description 5
- 229910052779 Neodymium Inorganic materials 0.000 claims description 5
- 229910045601 alloy Inorganic materials 0.000 claims description 5
- 239000000956 alloy Substances 0.000 claims description 5
- KBQHZAAAGSGFKK-UHFFFAOYSA-N dysprosium atom Chemical compound [Dy] KBQHZAAAGSGFKK-UHFFFAOYSA-N 0.000 claims description 5
- 229910052746 lanthanum Inorganic materials 0.000 claims description 5
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims description 5
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 claims description 5
- 229910052691 Erbium Inorganic materials 0.000 claims description 4
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 4
- UYAHIZSMUZPPFV-UHFFFAOYSA-N erbium Chemical compound [Er] UYAHIZSMUZPPFV-UHFFFAOYSA-N 0.000 claims description 4
- 229910052758 niobium Inorganic materials 0.000 claims description 4
- 239000010955 niobium Substances 0.000 claims description 4
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims description 4
- 229910052715 tantalum Inorganic materials 0.000 claims description 4
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 claims description 4
- 229910052726 zirconium Inorganic materials 0.000 claims description 4
- 229910052684 Cerium Inorganic materials 0.000 claims description 3
- 229910052693 Europium Inorganic materials 0.000 claims description 3
- 229910052689 Holmium Inorganic materials 0.000 claims description 3
- 229910052765 Lutetium Inorganic materials 0.000 claims description 3
- 229910052777 Praseodymium Inorganic materials 0.000 claims description 3
- 229910052772 Samarium Inorganic materials 0.000 claims description 3
- 229910052775 Thulium Inorganic materials 0.000 claims description 3
- 229910052769 Ytterbium Inorganic materials 0.000 claims description 3
- 229910052782 aluminium Inorganic materials 0.000 claims description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 3
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 claims description 3
- OGPBJKLSAFTDLK-UHFFFAOYSA-N europium atom Chemical compound [Eu] OGPBJKLSAFTDLK-UHFFFAOYSA-N 0.000 claims description 3
- 229910052735 hafnium Inorganic materials 0.000 claims description 3
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 claims description 3
- KJZYNXUDTRRSPN-UHFFFAOYSA-N holmium atom Chemical compound [Ho] KJZYNXUDTRRSPN-UHFFFAOYSA-N 0.000 claims description 3
- OHSVLFRHMCKCQY-UHFFFAOYSA-N lutetium atom Chemical compound [Lu] OHSVLFRHMCKCQY-UHFFFAOYSA-N 0.000 claims description 3
- PUDIUYLPXJFUGB-UHFFFAOYSA-N praseodymium atom Chemical compound [Pr] PUDIUYLPXJFUGB-UHFFFAOYSA-N 0.000 claims description 3
- KZUNJOHGWZRPMI-UHFFFAOYSA-N samarium atom Chemical compound [Sm] KZUNJOHGWZRPMI-UHFFFAOYSA-N 0.000 claims description 3
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 3
- 229910052721 tungsten Inorganic materials 0.000 claims description 3
- 239000010937 tungsten Substances 0.000 claims description 3
- NAWDYIZEMPQZHO-UHFFFAOYSA-N ytterbium Chemical compound [Yb] NAWDYIZEMPQZHO-UHFFFAOYSA-N 0.000 claims description 3
- 238000006243 chemical reaction Methods 0.000 claims description 2
- 230000004888 barrier function Effects 0.000 abstract description 9
- 238000005260 corrosion Methods 0.000 description 14
- 230000007797 corrosion Effects 0.000 description 14
- 238000005868 electrolysis reaction Methods 0.000 description 13
- 239000010408 film Substances 0.000 description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 9
- 239000002253 acid Substances 0.000 description 8
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 7
- 238000002441 X-ray diffraction Methods 0.000 description 7
- 239000000460 chlorine Substances 0.000 description 7
- 229910052801 chlorine Inorganic materials 0.000 description 7
- 238000000034 method Methods 0.000 description 7
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- 229910000428 cobalt oxide Inorganic materials 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
- 239000010970 precious metal Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 229910017052 cobalt Inorganic materials 0.000 description 4
- 239000010941 cobalt Substances 0.000 description 4
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 4
- 150000002739 metals Chemical class 0.000 description 4
- 239000012071 phase Substances 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 3
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical class Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- 229910052697 platinum Inorganic materials 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 235000011121 sodium hydroxide Nutrition 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- XTEGARKTQYYJKE-UHFFFAOYSA-M Chlorate Chemical class [O-]Cl(=O)=O XTEGARKTQYYJKE-UHFFFAOYSA-M 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 239000012267 brine Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000014509 gene expression Effects 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 239000011872 intimate mixture Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000008188 pellet Substances 0.000 description 2
- 230000002035 prolonged effect Effects 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 241000212376 Ammi Species 0.000 description 1
- 235000007034 Carum copticum Nutrition 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 229910017563 LaCrO Inorganic materials 0.000 description 1
- 229910001069 Ti alloy Inorganic materials 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- NFYLSJDPENHSBT-UHFFFAOYSA-N chromium(3+);lanthanum(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Cr+3].[La+3] NFYLSJDPENHSBT-UHFFFAOYSA-N 0.000 description 1
- QGUAJWGNOXCYJF-UHFFFAOYSA-N cobalt dinitrate hexahydrate Chemical compound O.O.O.O.O.O.[Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O QGUAJWGNOXCYJF-UHFFFAOYSA-N 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000006056 electrooxidation reaction Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 230000000135 prohibitive effect Effects 0.000 description 1
- 229910001404 rare earth metal oxide Inorganic materials 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- -1 terbium ions Chemical class 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- PMTRSEDNJGMXLN-UHFFFAOYSA-N titanium zirconium Chemical compound [Ti].[Zr] PMTRSEDNJGMXLN-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
- C25B11/075—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of a single catalytic element or catalytic compound
- C25B11/077—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of a single catalytic element or catalytic compound the compound being a non-noble metal oxide
- C25B11/0773—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of a single catalytic element or catalytic compound the compound being a non-noble metal oxide of the perovskite type
Definitions
- An electrode for electrochemical reactlons comprising a substrate of a film forming or barrier metal covered with a cobaltite of at least two rare earth metals, one '3 ggiff of the rare earth metals having a high atomic number
- the present invention concerns a new electrode which can be used in electrolytic cells serving for the production of chlorine, caustic soda or chlorates.
- the cells serving for the production of chlorine or caustic soda are either diaphragm cells or mercury cells.
- the chlorates are produced in a cell whose structure is similar to that of the diaphragm cells but which nevertheless has no diaphragm.
- the electrodes previously generally employed as anodes in electrolytic cells were frequently made of graphite. Their use has always entailed certain disadvantages resulting from their wear which causes an increase in the voltage necessary for the proper operation of the electrolysis cell as the result of the wear which increases in the distance between anodes and cathodes and the contamination of the electrolyte.
- anodes More recently it has been attempted to develop anodes from a metal having good resistance to corrosion by the electrolyte which metal is covered with an electrochemically active precious metal, the resulting composite then being subjected to a treatment which favors activation. These anodes are dimensionally stable and do not have the above-mentioned drawbacks.
- anodes of this type it has been proposed to employ a core of zirconium, zirconium-titanium alloy, tantalum or niobium covered with platinum.
- an anode of titanium covered with platinum Titanium, like the other core metals mentioned above, being a film forming or barrier metal capable of forming a film or barrier layer of oxide in the electrolysis solutions to protect its surface from corrosion at the places where the platinum is porous.
- electrodes have been produced of one of these film forming or barrier metals or alloys capable of forming a film or barrier layer, covered with an oxide of precious metal or with mixtures of oxides of precious and non-precious metals.
- perovskite is an oxygenated compound of two different metals which is well known in the literature and may be represented by the empirical formula:
- cobaltites have a relatively high electric conductivity which varies with the temperature, the rare earth metal playing an important role in the mechanism of conduction.
- the electrocatalytic power of these cobaltite compounds is not necessarily related to the perovskite structure, since there are numerous compounds having this structure, such as, for instance, LaCrO lanthanum chromite, which are without it.
- LaCrO lanthanum chromite which are without it.
- the compound LaCoO lanthanum cobaltite for instance, although having remarkable electrocatalytic properties, is entirely unsuitable to constitute an anode for an electrolysis cell as a result of the ease with which it passes into solution in slightly acid chlorinated medium. This defect decreases when the lanthanum is replaced by a rare earth of higher atomic number.
- the compounds LaCoO PrCoO NdCoO and GdCoO are prepared from an intimate mixture of the oxides of the stated. elements, which is calcined at 1200C. for 15 hours.
- the series of compounds thus prepared is analyzed by X-ray diffraction and is found in each case to be solely of the perovskite structure.
- the chemical resistivity in acid medium of these mixed oxides is then measured as follows:
- LaCoO PrCoO NdCoO GdCoO about about about about Time 1 hr. 30 hr. 400 hr. 500 hr.
- the new electrodes in accordance with the invention comprise a substrate of a film forming or barrier metal covered with a cobaltite compound described above which forms the surface of the electrode.
- This compound has the general formula in which Ln represents a rare earth metal of high atomic number, such as at least about 65, Ln a rare 4 earth metal of lower atomic number, such as below about 65, and x is a number between 0.001 and 0.999, and preferably between about 0.05 and 0.3.
- the new cobaltite compounds in accordance with the invention have a substantially higher resistance to acid corrosion than the known rare earth metal cobaltites, while having the same characteristics of conductivity and the same electrocatalytic properties.
- the rare earth metals which can be used are those listed in the Periodic Table of the Elements. Those of high atomic number comprise terbium, dysprosium, holmium, erbium, thulium, ytterbium and lutetium. The rare earths of lower atomic number comprise lanthanum, cerium, praseodymium, neodymium, samarium, europium and gadolinium.
- the substrate, or core, of the electrode is advantageously formed of film forming or barrier metal, that is to say, of metal forming a passivating layer of oxide which permits the passage of current only in the direction towards the cathode.
- film forming metals are well known and include, for example, titanium, tantalum, tungsten, hafnium, zirconium, aluminum, niobium and their alloys.
- Graphite can also be used and is intended to be included in the term film forming metal as used herein.
- the substrates may be solid pieces or thin, non-perforated plates. They may also be of perforated plates or metal gauze. Their shape is desirably that customarily employed for the anodes of electrolysis cells.
- the value of the ionic rays of the component rare earth metals of the cobaltite compound is important, and that it is not possible to combine merely any rare earth metals in any proportion.
- a rare earth having an ionic radius as small as that of erbium, it is necessary to introduce a rather large proportion of a rare earth metal having a rather high ionic radius such as that of neodymium.
- the rare earth cobaltite need not be limited to two rare earths, but may comprise three rare earths or even more, the essential factor being the retention of the perovskite structure from one or more rare earth metals leading to this structure with one or more rare earths not leading to it.
- These new compounds may be prepared like all the other cobaltites or perovskite structure by processes well known to the man skilled in the art. That is to say, thermolyzable organic or inorganic salts, oxides or hydroxides of the different elements are mixed, coprecipitated and cocrystallized. Then after the drying and crushing operations, the powder obtained, whether or not compacted, is calcined at a temperature between about 900 and about 1500C. for a period of time which may vary from 2 hours to 72 hours.
- the perovskite compounds which can be used for the electrodes of the invention may be prepared by any of the processes described in the literature. For example, by the process described in the journal American Mineralogist, Vol. 39 (l), 1954.
- EXAMPLE 1 Compounds are prepared of the general formula Gd e Tb Coo in which x is the quantity of Gd ions in the gadolinium cobaltite which are replaced by terbium ions.
- the cobaltite thus prepared is then deposited on a titanium plate of 10 mm. width by 30 mm. length and 1 mm. thickness which has been previously cleaned by sanding, washed with distilled water. and dried.
- a suspension of the cobaltite is prepared in the following manner: To 1 gram of powder there is added 1 gram of hydrated cobalt nitrate hexahydrate, 1 ml. of water and 1 ml. of isopropyl alcohol. The paste obtained is agitated vigorously until homogeneous suepension is obtained, the agitation being maintained during the production of the deposit. A layer of the suspension of the cobaltite is applied on the surface of the titanium plate by brush. After drying for 5 min. in an oven at 100C, the resulting electrode is kept for 10 min. in a furnace at a temperature of 400C. while it is swept by air. This operation is repeated 20 times. The amount of product deposited is 40 mg./cm The deposit on the electrode consists of cobaltite and 20% cobalt oxide.
- the electrode thus prepared is placed in an electrolysis cell for the manufacture of chlorine and caustic soda, in which the electrolyte is a solution of 300 grams per liter of sodium chloride maintained at 80C. and a pH of 4.
- a current such as to produce an anodic current density of 25 amperes per square decimeter is then passed into the cell; the anodic oxidation voltage of the chloride ions is l millivolts when referred to a saturated calomel electrode. After 1000 hours of electrolysis, the anode potential remains unchanged.
- EXAMPLE 2 In accordance with the procedure of Example 1, compounds are prepared of the general formula Gd ,Dy CoO from gadolinium, dysprosium and cobalt oxides, the quantities of which, as a function of x, are summarized in Table 4, below:
- An electrode is prepared with a surface of Gd Dy C on a titanium plate in accordance with the pro- 1 cedure of Example 1. This electrode is used as electrolysis anode for the manufacture of chlorine. For a brine of 300 grams per liter at 80C. and a pH of 4, there is obtained a strong liberation of chlorine with a current density of 25 amperes per square decimeter, under a voltage of 100 millivolts when referred to a saturated calomel electrode. After a prolonged period of electrolysis, the anode potential remains unchanged.
- An electrode is prepared having a surface of Nd Tb CoO on a plate of titanium by means of an organic or inorganic binder in accordance with a procedure substantially the same as that of Example 1.
- This electrode is used as electrolysis anode for the manufacture of chlorine.
- An electrode for electrochemical reactions comprising a substrate covered with a compound having a perovskite structure, characterized by the fact that the substrate is of a film forming metal and the compound of perovskite structure is a cobaltite of rare earths having the general formula Ln Ln ,CoO in which Ln has an atomic number of at least about and Ln has an atomic number below about 65, wherein x is between 0.001 and 0.999.
- Ln is a member selected from the class consisting of lanthanum, cerium, praseodymium, neodymium, Samarium, europium and gadolinium.
- the film forming metal substrate is a member selected from the class consisting of titanium, tantalum, tungsten, hafnium, zirconium, aluminum, niobium and their alloys.
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Electrodes For Compound Or Non-Metal Manufacture (AREA)
- Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR7326694A FR2237986B1 (cg-RX-API-DMAC7.html) | 1973-07-20 | 1973-07-20 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US3917525A true US3917525A (en) | 1975-11-04 |
Family
ID=9122912
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US486051A Expired - Lifetime US3917525A (en) | 1973-07-20 | 1974-07-05 | Electrode for electrochemical reactions |
Country Status (14)
| Country | Link |
|---|---|
| US (1) | US3917525A (cg-RX-API-DMAC7.html) |
| JP (1) | JPS5331478B2 (cg-RX-API-DMAC7.html) |
| AT (1) | AT331820B (cg-RX-API-DMAC7.html) |
| BE (1) | BE817795A (cg-RX-API-DMAC7.html) |
| BR (1) | BR7405900D0 (cg-RX-API-DMAC7.html) |
| CA (1) | CA1048230A (cg-RX-API-DMAC7.html) |
| CH (1) | CH587927A5 (cg-RX-API-DMAC7.html) |
| FR (1) | FR2237986B1 (cg-RX-API-DMAC7.html) |
| GB (1) | GB1437919A (cg-RX-API-DMAC7.html) |
| IT (1) | IT1016923B (cg-RX-API-DMAC7.html) |
| NL (1) | NL178612C (cg-RX-API-DMAC7.html) |
| NO (1) | NO138633C (cg-RX-API-DMAC7.html) |
| SE (1) | SE391743B (cg-RX-API-DMAC7.html) |
| SU (1) | SU557763A3 (cg-RX-API-DMAC7.html) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3992278A (en) * | 1975-09-15 | 1976-11-16 | Diamond Shamrock Corporation | Electrolysis cathodes having a melt-sprayed cobalt/zirconium dioxide coating |
| US4010091A (en) * | 1975-05-30 | 1977-03-01 | Rhone-Poulenc Industries | Novel electrode for electrolysis cell |
| US4042483A (en) * | 1973-07-20 | 1977-08-16 | Rhone-Progil | Electrolysis cell electrode and method of preparation |
| US4076611A (en) * | 1976-04-19 | 1978-02-28 | Olin Corporation | Electrode with lanthanum-containing perovskite surface |
| US4313813A (en) * | 1979-10-09 | 1982-02-02 | Ppg Industries, Inc. | Fixed bed oxygen depolarized cathode chlor-alkali cell |
| US4342792A (en) * | 1980-05-13 | 1982-08-03 | The British Petroleum Company Limited | Electrodes and method of preparation thereof for use in electrochemical cells |
| CN102304724A (zh) * | 2011-09-21 | 2012-01-04 | 山东大学 | 稀土镨和镝联合掺杂纳米钛基二氧化锡-锑双涂层电极的制备方法 |
| CN104593816A (zh) * | 2013-11-01 | 2015-05-06 | 南京宁科环保科技有限公司 | 一种利用稀土铕改性钛基二氧化锡涂层电极的制备方法 |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| RU2553460C2 (ru) * | 2013-11-13 | 2015-06-20 | Федеральное государственное бюджетное образовательное учреждение высшего образования "Московский государственный университет имени М.В. Ломоносова" (МГУ) | Катодные материалы для твердооксидных топливных элементов на основе никельсодержащих слоистых перовскитоподобных оксидов |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3329594A (en) * | 1964-12-08 | 1967-07-04 | Pittsburgh Plate Glass Co | Electrolytic production of alkali metal chlorates |
| US3801490A (en) * | 1972-07-18 | 1974-04-02 | Ppg Industries Inc | Pyrochlore electrodes |
| US3804740A (en) * | 1972-02-01 | 1974-04-16 | Nora Int Co | Electrodes having a delafossite surface |
-
1973
- 1973-07-20 FR FR7326694A patent/FR2237986B1/fr not_active Expired
-
1974
- 1974-07-05 US US486051A patent/US3917525A/en not_active Expired - Lifetime
- 1974-07-17 AT AT591974A patent/AT331820B/de not_active IP Right Cessation
- 1974-07-17 NO NO742604A patent/NO138633C/no unknown
- 1974-07-17 BR BR5900/74A patent/BR7405900D0/pt unknown
- 1974-07-17 NL NLAANVRAGE7409649,A patent/NL178612C/xx not_active IP Right Cessation
- 1974-07-18 BE BE146678A patent/BE817795A/xx not_active IP Right Cessation
- 1974-07-18 CA CA74205028A patent/CA1048230A/en not_active Expired
- 1974-07-18 SE SE7409408A patent/SE391743B/xx not_active IP Right Cessation
- 1974-07-18 SU SU2044226A patent/SU557763A3/ru active
- 1974-07-19 JP JP8309074A patent/JPS5331478B2/ja not_active Expired
- 1974-07-19 GB GB3213174A patent/GB1437919A/en not_active Expired
- 1974-07-19 IT IT52186/74A patent/IT1016923B/it active
- 1974-07-19 CH CH1000374A patent/CH587927A5/xx not_active IP Right Cessation
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3329594A (en) * | 1964-12-08 | 1967-07-04 | Pittsburgh Plate Glass Co | Electrolytic production of alkali metal chlorates |
| US3804740A (en) * | 1972-02-01 | 1974-04-16 | Nora Int Co | Electrodes having a delafossite surface |
| US3801490A (en) * | 1972-07-18 | 1974-04-02 | Ppg Industries Inc | Pyrochlore electrodes |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4042483A (en) * | 1973-07-20 | 1977-08-16 | Rhone-Progil | Electrolysis cell electrode and method of preparation |
| US4010091A (en) * | 1975-05-30 | 1977-03-01 | Rhone-Poulenc Industries | Novel electrode for electrolysis cell |
| US3992278A (en) * | 1975-09-15 | 1976-11-16 | Diamond Shamrock Corporation | Electrolysis cathodes having a melt-sprayed cobalt/zirconium dioxide coating |
| US4076611A (en) * | 1976-04-19 | 1978-02-28 | Olin Corporation | Electrode with lanthanum-containing perovskite surface |
| US4133778A (en) * | 1976-04-19 | 1979-01-09 | Olin Corporation | Electrode with lanthanum-containing perovskite surface |
| US4313813A (en) * | 1979-10-09 | 1982-02-02 | Ppg Industries, Inc. | Fixed bed oxygen depolarized cathode chlor-alkali cell |
| US4342792A (en) * | 1980-05-13 | 1982-08-03 | The British Petroleum Company Limited | Electrodes and method of preparation thereof for use in electrochemical cells |
| CN102304724A (zh) * | 2011-09-21 | 2012-01-04 | 山东大学 | 稀土镨和镝联合掺杂纳米钛基二氧化锡-锑双涂层电极的制备方法 |
| CN102304724B (zh) * | 2011-09-21 | 2013-06-26 | 山东大学 | 稀土镨和镝联合掺杂纳米钛基二氧化锡-锑双涂层电极的制备方法 |
| CN104593816A (zh) * | 2013-11-01 | 2015-05-06 | 南京宁科环保科技有限公司 | 一种利用稀土铕改性钛基二氧化锡涂层电极的制备方法 |
| CN104593816B (zh) * | 2013-11-01 | 2017-07-28 | 科盛环保科技股份有限公司 | 一种利用稀土铕改性钛基二氧化锡涂层电极的制备方法 |
Also Published As
| Publication number | Publication date |
|---|---|
| NO138633C (no) | 1978-10-11 |
| FR2237986B1 (cg-RX-API-DMAC7.html) | 1977-05-13 |
| SU557763A3 (ru) | 1977-05-05 |
| SE391743B (sv) | 1977-02-28 |
| CH587927A5 (cg-RX-API-DMAC7.html) | 1977-05-13 |
| NL7409649A (nl) | 1975-01-22 |
| AT331820B (de) | 1976-08-25 |
| JPS5071582A (cg-RX-API-DMAC7.html) | 1975-06-13 |
| NO138633B (no) | 1978-07-03 |
| BR7405900D0 (pt) | 1975-05-13 |
| SE7409408L (cg-RX-API-DMAC7.html) | 1975-01-21 |
| JPS5331478B2 (cg-RX-API-DMAC7.html) | 1978-09-02 |
| DE2434412B2 (de) | 1976-07-29 |
| CA1048230A (en) | 1979-02-13 |
| DE2434412A1 (de) | 1975-02-13 |
| BE817795A (fr) | 1975-01-20 |
| NL178612B (nl) | 1985-11-18 |
| IT1016923B (it) | 1977-06-20 |
| FR2237986A1 (cg-RX-API-DMAC7.html) | 1975-02-14 |
| GB1437919A (en) | 1976-06-03 |
| NL178612C (nl) | 1986-04-16 |
| ATA591974A (de) | 1975-12-15 |
| NO742604L (cg-RX-API-DMAC7.html) | 1975-02-17 |
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