EP0035017A1 - Catalytically active anode - Google Patents
Catalytically active anodeInfo
- Publication number
- EP0035017A1 EP0035017A1 EP80900603A EP80900603A EP0035017A1 EP 0035017 A1 EP0035017 A1 EP 0035017A1 EP 80900603 A EP80900603 A EP 80900603A EP 80900603 A EP80900603 A EP 80900603A EP 0035017 A1 EP0035017 A1 EP 0035017A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- anode
- metal
- anode according
- silicate
- binder
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Withdrawn
Links
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims abstract description 17
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 11
- 239000010941 cobalt Substances 0.000 claims abstract description 11
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000000758 substrate Substances 0.000 claims abstract description 11
- 239000011230 binding agent Substances 0.000 claims abstract description 9
- 239000006185 dispersion Substances 0.000 claims abstract description 8
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 15
- 229910052751 metal Inorganic materials 0.000 claims description 12
- 239000002184 metal Substances 0.000 claims description 12
- 229910052914 metal silicate Inorganic materials 0.000 claims description 12
- 229910052742 iron Inorganic materials 0.000 claims description 7
- 239000007864 aqueous solution Substances 0.000 claims description 4
- 238000005868 electrolysis reaction Methods 0.000 claims description 4
- 230000002209 hydrophobic effect Effects 0.000 claims description 4
- 238000000034 method Methods 0.000 claims description 4
- 229910052609 olivine Inorganic materials 0.000 claims description 4
- 239000010450 olivine Substances 0.000 claims description 4
- 150000004760 silicates Chemical class 0.000 claims description 4
- KKEBXNMGHUCPEZ-UHFFFAOYSA-N 4-phenyl-1-(2-sulfanylethyl)imidazolidin-2-one Chemical compound N1C(=O)N(CCS)CC1C1=CC=CC=C1 KKEBXNMGHUCPEZ-UHFFFAOYSA-N 0.000 claims description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 2
- 239000003513 alkali Substances 0.000 claims description 2
- 239000011248 coating agent Substances 0.000 claims description 2
- 238000000576 coating method Methods 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 239000010949 copper Substances 0.000 claims description 2
- 239000010970 precious metal Substances 0.000 claims description 2
- 229910052596 spinel Inorganic materials 0.000 claims description 2
- 239000011029 spinel Substances 0.000 claims description 2
- 229910052723 transition metal Inorganic materials 0.000 claims description 2
- 150000003624 transition metals Chemical class 0.000 claims description 2
- 239000003792 electrolyte Substances 0.000 claims 1
- 239000001257 hydrogen Substances 0.000 abstract description 5
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 4
- 239000004744 fabric Substances 0.000 abstract 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 10
- 239000000377 silicon dioxide Substances 0.000 description 5
- -1 polytetrafluoroethylene Polymers 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 206010010144 Completed suicide Diseases 0.000 description 2
- 229910002651 NO3 Inorganic materials 0.000 description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 2
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 2
- FMQXRRZIHURSLR-UHFFFAOYSA-N dioxido(oxo)silane;nickel(2+) Chemical compound [Ni+2].[O-][Si]([O-])=O FMQXRRZIHURSLR-UHFFFAOYSA-N 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
- 229910052720 vanadium Inorganic materials 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 241000220317 Rosa Species 0.000 description 1
- 239000004115 Sodium Silicate Substances 0.000 description 1
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 1
- AVFZJFVTJSWXMI-UHFFFAOYSA-N [Co+4].[O-][Si]([O-])([O-])[O-] Chemical group [Co+4].[O-][Si]([O-])([O-])[O-] AVFZJFVTJSWXMI-UHFFFAOYSA-N 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000012267 brine Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 229910000428 cobalt oxide Inorganic materials 0.000 description 1
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000010411 electrocatalyst Substances 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 229910052735 hafnium Inorganic materials 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 229910000480 nickel oxide Inorganic materials 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000000634 powder X-ray diffraction Methods 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 1
- 238000001778 solid-state sintering Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 238000010561 standard procedure Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 229910000326 transition metal silicate Inorganic materials 0.000 description 1
- 229910052726 zirconium Inorganic materials 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
-
- 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
Definitions
- metal suicide the metal being one of Pt, Pd, Ir, Eh, Cr, Co, Ni, Ru, Ti, V, Zr, Nb, Hf, Ta and V.
- the invention consists in a catalytically active anode comprising at its surface an at least semiconductive water- insoluble metal silicate.
- the anode is made by dispersing the metal silicate in a non-conductive binder, and applying the dispersion to a conductive substrate.
- the silicate is reduced sufficiently to improve its electrical conductivity.
- the binder is hydrophobic, for example polytetrafluoroethylene, but the dispersion as a whole should not be excessively hydrophobic.
- the metal silicate may have a spinel or olivine structure, both of which are reported to have been synthesised.
- the olivine is convenient. It is preferably cobalt orthosilicate (Co SiO. )
- the substrate is preferably in the form of an electrically conductive sheet (foraminate or otherwise), slit metal or mesh, preferably of nickel. If of iron, the substrate preferably contains under 1.5% (more preferably under -0.3%) of carbon.
- the weight ratio of binder to metal silicate is from l-3 > more preferably from 1:5 > to 1:20 and the dispersion is preferably applied to give a coating of from 5 m 9 to 50mg of the metal silicate per square centimetre of the substrate.
- the invention extends to a catalytically active anode made as set forth above, and to an electrolytic cell including a cathode and such an anode. The invention further extends to a method of electrolysis using this cell, especially of aqueous solutions, e.g. aqueous alkali. The invention will now be described by way of example. MAKING AN ANODE
- transition metal silicates include precipitation from sodium silicate solution, and gelling using tetraethyl orthosilicate, it was found that solid state sintering gave the best results.
- Cobalt nitrate was ground with a stoichiometric amount of silica with a pestle and mortar.
- the mixture of cobalt nitrate and silica was transferred to an evaporating basin, gently heated to allow the nitrate to dissolve in its own water of crystallis- ation and then vigorously heated by bunsen burner to dry and decompose the nitrate to its oxide.
- the resultant powder was o , ground again and then heated at 1000 C for 24 hours, to promote the reaction 2Co0 + SiO —>Co SiO..
- the product was ground again, washed with 5M KOH and then with concentrated HN0 to remove any unreacted silica or cobalt oxide, then washed with water, dried, ground again and put in a dry sample bottle. That the product was cobalt silicate (olivine structure) was confirmed by X-ray powder diffraction.
- the electrode so formed was dried and cured for 1 hour at 300 C. Initially a cobalt silicate: polytetrafluoroethylene ratio of 10:3 was used, but as this proved to be too hydrophobic, the present electrode used a ratio of 10:1, giving a cobalt silicate loading of 21 mg/ /cm2.
- ELECTROLYSIS An aqueous solution of 5 KOH was electolysed at 40 C in a cell having a nickel mesh cathode and the above anode. (The anode had previously been anodised for 2 hours at 2V vs the dynamic hydrogen electrode, to activate it, possibly by forming higher oxides on its surface and hydr ⁇ phiusing it. ) The current was held at 1 amp. Oxygen was evolved at the anode, at which the voltage vs. the dynamic hydrogen electrode rose from an initial' 1700mV, neglecting early fluctuations, to 174 ⁇ mV after 40 days, possibly due to formation of a poorly conductive nickel oxide at the interface between screen and cobalt silicate. An identical cell (but with cobalt silicate loading of l4 mg/cm ) was run at 25 C, 50 C and 70 C at up to 2-g-A/cm . At
- iron silicate might be corroding at up to 6 mg/cm /week at
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Electrodes For Compound Or Non-Metal Manufacture (AREA)
- Silicates, Zeolites, And Molecular Sieves (AREA)
- Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
GB7912624 | 1979-04-10 | ||
GB7912624 | 1979-04-10 |
Publications (1)
Publication Number | Publication Date |
---|---|
EP0035017A1 true EP0035017A1 (en) | 1981-09-09 |
Family
ID=10504466
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP80900603A Withdrawn EP0035017A1 (en) | 1979-04-10 | 1980-10-23 | Catalytically active anode |
Country Status (4)
Country | Link |
---|---|
EP (1) | EP0035017A1 (cs) |
JP (1) | JPS56500377A (cs) |
GB (1) | GB2048945A (cs) |
WO (1) | WO1980002163A1 (cs) |
Families Citing this family (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CA2020482C (en) * | 1990-07-05 | 1999-10-12 | Sellathurai Suppiah | Supported high silica zeolites |
JP5729163B2 (ja) * | 2011-06-24 | 2015-06-03 | トヨタ自動車株式会社 | 負極活物質及び負極活物質の製造方法 |
Family Cites Families (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE1915951A1 (de) * | 1969-03-28 | 1970-10-08 | Basf Ag | Verfahren zur Herstellung von Elektroden |
US3711382A (en) * | 1970-06-04 | 1973-01-16 | Ppg Industries Inc | Bimetal spinel surfaced electrodes |
US3798063A (en) * | 1971-11-29 | 1974-03-19 | Diamond Shamrock Corp | FINELY DIVIDED RuO{11 {11 PLASTIC MATRIX ELECTRODE |
US3963593A (en) * | 1972-09-15 | 1976-06-15 | Ppg Industries, Inc. | Electrodes having silicide surface |
GB1448989A (en) * | 1972-12-13 | 1976-09-08 | Nat Res Dev | Coated substrates for use as corrosion resistant electrodes for electrochemical use |
-
1980
- 1980-04-10 JP JP50073480A patent/JPS56500377A/ja active Pending
- 1980-04-10 WO PCT/GB1980/000063 patent/WO1980002163A1/en not_active Application Discontinuation
- 1980-04-10 GB GB8011904A patent/GB2048945A/en not_active Withdrawn
- 1980-10-23 EP EP80900603A patent/EP0035017A1/en not_active Withdrawn
Non-Patent Citations (1)
Title |
---|
See references of WO8002163A1 * |
Also Published As
Publication number | Publication date |
---|---|
WO1980002163A1 (en) | 1980-10-16 |
JPS56500377A (cs) | 1981-03-26 |
GB2048945A (en) | 1980-12-17 |
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Legal Events
Date | Code | Title | Description |
---|---|---|---|
PUAI | Public reference made under article 153(3) epc to a published international application that has entered the european phase |
Free format text: ORIGINAL CODE: 0009012 |
|
17P | Request for examination filed |
Effective date: 19810508 |
|
AK | Designated contracting states |
Designated state(s): DE FR GB |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: THE APPLICATION IS DEEMED TO BE WITHDRAWN |
|
18D | Application deemed to be withdrawn |
Effective date: 19830218 |