EP2055807B1 - Électrode d'évolution de l'oxygène - Google Patents

Électrode d'évolution de l'oxygène Download PDF

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Publication number
EP2055807B1
EP2055807B1 EP07119704A EP07119704A EP2055807B1 EP 2055807 B1 EP2055807 B1 EP 2055807B1 EP 07119704 A EP07119704 A EP 07119704A EP 07119704 A EP07119704 A EP 07119704A EP 2055807 B1 EP2055807 B1 EP 2055807B1
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EP
European Patent Office
Prior art keywords
oxide
cationic
electrode
oxygen evolution
anode
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EP07119704A
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German (de)
English (en)
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EP2055807A1 (fr
Inventor
Koji Hashimoto
Ahmed Abd El-Moneim
Naokazu Kumagai
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Hashimoto Koji
Daiki Ataka Engineering Co Ltd
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Daiki Ataka Engineering Co Ltd
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Priority to DE602007007783T priority Critical patent/DE602007007783D1/de
Priority to EP07119704A priority patent/EP2055807B1/fr
Publication of EP2055807A1 publication Critical patent/EP2055807A1/fr
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    • 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
    • C25B11/055—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the substrate or carrier material
    • C25B11/057—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the substrate or carrier material consisting of a single element or compound
    • 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
    • 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
    • C25B11/054—Electrodes comprising electrocatalysts supported on a carrier
    • 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
    • C25B11/091—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of at least one catalytic element and at least one catalytic compound; consisting of two or more catalytic elements or catalytic compounds
    • C25B11/093—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of at least one catalytic element and at least one catalytic compound; consisting of two or more catalytic elements or catalytic compounds at least one noble metal or noble metal oxide and at least one non-noble metal oxide

Definitions

  • the present invention concerns an anode for oxygen evolution without forming chlorine in electrolysis of chloride-containing aqueous solutions including seawater.
  • seawater electrolysis is performed to produce sodium hypochlorite by the reaction of chlorine formed on the anode with sodium hydroxide formed on the cathode in addition to the formation of hydrogen on the cathode.
  • anodes made by coating titanium with an oxide of an element or elements of the platinum group hereinafter referred to as "platinum group element(s)) as the high performance electrodes.
  • the above-described previous invention is based on the findings that, in production of oxygen evolution anode, calcination of Mn salt coated on the electroconductive substrate leads to formation of Mn 2 O 3 and that inclusion of Mo and/or W in Mn 2 O 3 enhances the oxygen evolution efficiency.
  • calcination temperature is not sufficiently high, stability of the electrode is insufficient due to insufficient crystal growth, but even at high temperatures Mn cannot be oxidized to such a high valence as three or higher because of decomposition of high valence Mn oxide.
  • the inventors made the following inventions and the inventions were disclosed. They concern the electrolytic cell using the above-described anode (Japanese Patent Disclosure No. 11-256383 ), the electrode assembly using combination of the electrode and a diode (Japanese Patent Disclosure No. 11-256384 ) and a method of producing the anode (Japanese Patent Disclosure No. 11-256385 ), Furthermore, the inventors found that the electrode in which Fe is added to Mn-Mo, Mn-W or Mn-Mo-W oxide was effective as oxygen evolution anode in the solutions containing chloride ion in a wide temperature range up to just below the boiling point of water, (Japanese Patent Disclosure No. 2003-19267 ). Another patent application was filed for the modified technology of producing the anode including the preparation method of the titanium substrate (Japanese Patent Disclosure No. 2007-138254 ).
  • the anodically deposited oxide consist of 0.2-20 cationic % of Mo and/or W, in which 0.1-3 mol % thereof is substituted with Sn, and the balance of Mn.
  • the anode thus formed showed high performance for oxygen evolution in aqueous solutions containing chloride ion.
  • titanium is used as the electroconductive substrate on which the electroactive catalysts containing Mn are coated.
  • Such an electrode made by coating titanium with oxide or oxide of the platinum group element(s) is known as dimensionally stable anode and has been used as the anode for electrolysis and electrodeposition.
  • the inventors in view of the preferable characteristics for the coating layer on the titanium substrate that it has the same rutile structure as TiO 2 and is stable without being dissolved even under highly oxidizing condition of anodic polarization, and noted that an oxide of tin, SnO 2 , has the same rutile structure as TiO 2 and is stable without dissolution under highly oxidizing condition, hit upon an idea of using SnO 2 together with the oxide of the platinum group element(s) in the intermediate layer.
  • the electronic conductivity of SnO 2 is not sufficiently high, this problem was overcome by the inventors' discovery that the electronic conductivity can be enhanced by addition of Sb, and hence, that it is advisable to_use Sn together with Sb.
  • the electrode based on the above-described idea and_discovery consists of a titanium substrate and multiple oxide of the platinum group-element(s), and Sb and Sn.
  • the electrode having the multiple oxide as the electrocatalyst can be used in various electrochemical reactions such as electrolysis and electrodeposition.
  • the electrode according to the invention is an anode used for electrochemical reactions made by coating an electroconductive substrate of titanium with a layer of metal oxide as the electrocatalyst, in which the metal oxide consist of multiple oxide of Sn and Sb, and the platinum group element(s).
  • the cationic Sn/Sb ratio is in the range of 1-40, and the sum of Sn and Sb in the electrocatalyst is 90 cationic % or less, preferably 1-70 cationic %, and the balance of the oxide of the platinum group element(s).
  • the objective of the present invention based on the recent knowledge of the inventors is to provide an oxygen evolution anode made by coating an electroconductive substrate such as titanium with an intermediate layer consisting of precious metal oxide and forming an electrocatalyst consisting of oxide of Mn and Mo and/or W thereon, in which necessary amount of the precious metal(s) in the intermediate layer is decreased so as to lower the manufacturing cost and to mitigate shortage of the precious metal resources, and at the same time to realize improvement in the performance and durability of the electrocatalyst.
  • the oxygen evolution electrode of the present invention is an electrode made by forming on a substrate an intermediate layer and an electrocatalyst layer in this order and is used for evolving oxygen without chlorine formation in electrolysis of aqueous solution containing chloride ion, in which the intermediate layer prepared by calcinations consists of multiple oxide of the platinum group element(s), Sn and Sb with the Sn/Sb ratio of 1-40 and with the sum of Sn and Sb of 90 cationic % or less, and the electrocatalyst prepared by anodic deposition consists of 0.1-3 cationic % of Sn, 0.2-20 cationic % of Mo and/or W and the balance of Mn as the main component.
  • Corrosion resistant titanium is suitable for the conductive substrate of the electrode because it is exposed to highly oxidizing environment.
  • the substrate is subjected to treatments for removing the air-formed oxide film by acid washing and for surface roughening by etching to enhance adhesion of the electrocatalyst.
  • the titanium substrate is then coated by repeated brushing of the solution such as butanol solution of adequate concentrations of salt(s) of platinum group element(s), and Sn and Sb, and subsequent drying followed by calcinations at 550°C.
  • the electrode with the electrocatalyst of multiple oxide consisting of Sn, Sb and one or more of platinum group elements is prepared.
  • the platinum group element(s) are the basic component of the intermediate layer of the present invention, and Ru, Rh, Pd, Os, Ir and Pt form MO 2 type oxide by heat treatment in air. These oxide except PtO 2 have the same rutile structure as TiO 2 and SnO 2 and form solid solution with them.
  • the lattice constants of "a"-axis and "c"-axis of PtO 2 are quite close to those of TiO 2 and SnO 2 , and hence, PtO 2 forms a single phase oxide with TiO 2 and SnO 2 .
  • the oxide of [platinum group element(s)-Sn-Sb] forming the intermediate layer are multiple oxide of single phase, and hence, for formation of the single phase oxide the compositions can be chosen arbitrarily. It is desirable to decrease the amount(s) of platinum group element(s) by increasing the relative amounts of Sn and Sb thereto so as to decrease the cost and to save the resources. However, excess addition of Sn and Sb lowers the performance of the electrodes, and hence, the sum of Sn and Sb in the oxide constituting the intermediate layer should be 90 cationic % or less, preferably, 70 cationic % or less.
  • the electrode is not superior to the electrodes with only platinum oxide as the intermediate layer, and hence, the sum of Sn and Sb in the oxide should be 1 cationic % or more.
  • the suitable sum of Sn and Sb is in the range of 1-70 cationic % and the most suitable sum is in the range of 30-60 cationic %
  • Sb is added to enhance the electric conductivity that is insufficient in multiple oxide consisting only of platinum group element(s) and Sb. If Sb is added in such amount that the cationic Sn/Sb ratio is 40 or lower, the oxide formed have sufficient electric conductivity, and hence, the Sn/Sb ratio is chosen to_be 40 or lower. However, excess addition of Sb rather decreases the electric conductivity, and hence, the added Sb should be at such a level that the cationic Sn/Sb ratio may be unity or more.
  • electrocatalyst by anodic deposition can be carried out on the thus prepared substrate in a heated electrolytic solution of MnSO 4 -SnCl 4 with Na 2 MoO 4 and/or Na 2 WO 4 , the pH of which is adjusted by addition of sulfuric acid.
  • composition of the multiple oxide electrocatalyst is defined above.
  • Sn increases oxygen evolution activity and durability of_the electrode by constituting the multiple oxide with Mn and W and/or Mo. This effect appears with the addition of 0.1 cationic % or more of Sn, and increases at a higher Sn content. However, excess addition of Sn rather decreases the oxygen evolution efficiency, and hence, the content of Sn is limited to be at highest 3 cationic %.
  • the intermediate layer contacting electroconductive substrate made of titanium is multiple oxide layer of SnO 2 and MO 2 (M is platinum group element(s)) of the same rutile structure as TiO 2 , and hence, prevent s continuously formation of insulating oxide film on the titanium substrate. Furthermore, because of the smaller amount of platinum group element(s) in the intermediate layer, the manufacturing cost is low and the problem of the resources is mitigated.
  • the electrocatalyst layer on the intermediate layer is multiple oxide layer of Mn-Mo and/or W-Sn-Sb, and the electrode performance is improved in comparison with the electrode with multiple oxide of Mn-Mo and/or W only. The life of the electrode is significantly prolonged due to prolonged function of the intermediate layer and enhanced durability of the electrocatalyst.
  • a titanium mesh made by punching a plate was immersed in 0.5 M HF solution for 5 min. to remove the surface oxide film, and then, subjected to etching in 11.5 M H 2 SO 4 solution at 80°C to increase the surface roughness until hydrogen evolution ceased due to the coverage of the surface with titanium sulfate. Titanium sulfate on the titanium surface was washed away by flowing tap water for about 1 hr. Just before coating the intermediate layer the titanium mesh was ultrasonically rinsed in deionized water.
  • the above titanium mesh with the effective surface area of 20 cm 2 was coated by brushing mixed butanol solutions of 4.0 ml of 5 M K 2 IrCl 6 , 5.33 ml of 5 M SnCl 4 and 0.67 ml of 5 M SbCl 6 , dried at 90°C for 5 min. and calcinated for conversion to oxide at 550°C for 10 min. The procedures were repeated until the weight of oxide increased to 45 g/m 2 .
  • the electrode substrate was obtained by final calcination at 550°C for 60 min.
  • the cationic composition of the intermediate layer thus formed was determined by EPMA.
  • the cationic %'s of Ir, Sn and Sb in the electrocatalyst layer were 65.0, 28.5 and 6.5%, respectively.
  • a mixed solution of the composition of 0.2 M MnSO 4 -0.003 M Na 2 MoO 4 -0.006 M SnCl 4 was prepared, and the pH was adjusted to -0.1 by addition of sulfuric acid, and the solution was warmed to 90°C.
  • Ir-Sn-Sb triple oxide-coated titanium substrate was carried out in the above electrolysis mixed solution at the current density of 600 A/m 2 for 60 min.
  • the electrode thus prepared electrolysis was carried out in 0.5 M NaCl solution of pH 8.7 at 1000 A/m 2 for 1000 Coulombs, and then the chlorine evolution efficiency was analyzed by iodimetric titration. No chlorine evolution was detected with a consequent 100% oxygen evolution efficiency. Even after electrolysis for 1400 h in the above-mentioned solution the oxygen evolution efficiency was 98% or highe r . It was ascertained that the electrode of the present invention has high activity for oxygen evolution and excellent durability.
  • Example 2 The same surface treatments as in Example 1, i.e., removal of the surface film, etching for surface roughening, rinsing with water and ultrasonic rinsing were applied to other punched titanium meshes of the effective surface area of 20 cm 2 , and the resulting mesh was used as the anode substrate.
  • Respective 5 M butanol solutions of RuCl 3 , RhCl 3 , PdCl 3 , OsCl 3 , K 2 IrCl 6 and K 2 PtCl 6 were prepared as the materials of the platinum group elements.
  • the titanium meshes were coated by repeated brushing of the mixed solutions, drying at 90°C for 5 min. and calcination for conversion to oxide at 550°C for 10 min. until the weight of oxide increased to 45 g/m 2 .
  • Substrates of the electrode were obtained by final calcination at 550°C for 60 min.
  • the cationic compositions of the intermediate layers thus formed were determined by EPMA. The results are shown in Table 1.
  • the electrolysis was carried out in 0.5 M NaCl solution of pH 8.7 at current density of 1000 A/m 2 for 1000 Coulombs, and then, an attempt was made to obtain the oxygen evolution efficiency from the difference between the amount of charge passed and the amount of chlorine formation obtained by iodimetric titration. No chlorine evolution was detected, and thus, all the electrodes showed 100 % oxygen evolution efficiency as shown in Table 1. It is, therefore, concluded that the electrode of the present invention is highly active for oxygen evolution as the anode in the electrolysis of solutions containing chloride ion. Table 1 No.
  • Example 2 The same surface treatments as in Example 1, i.e., removal of the surface film, etching for surface roughening, rinsing with water and ultrasonic rinsing were applied to the punched titanium of the effective surface area of 20 cm 2 .
  • the above titanium meshes were coated by brushing with mixed butanol solutions of different mixed ratios of 5 M K 2 IrCl 6 , 5 M SnCl 4 and 5 M SbCl 6 , dried at 90°C for 5 min. and calcined for conversion to oxide at 550°C for 10 min. The procedures were repeated until the weight of the oxide increased to 45 g/m 2 . Substrates of the electrode were obtained by final calcination at 550°C for 60 min. The cationic compositions of the intermediate layers thus formed were determined by EPMA. The cationic % of Ir, Sn and Sb are shown in Table 2.
  • the anodic deposition was carried out in an electrolytic solution of the composition of 0.2 M MnSO 4 -0.003 M Na 2 MoO 4 -0.006 M SnCl 4 solution, the pH of which was adjusted to -0.1 by addition of sulfuric acid, and warmed to 90°C, on the above-prepared anode with the intermediate layer of the oxides at a current density of 600 A/m 2 .
  • the electrolysis was carried out in 0.5 M NaCl solution of pH 8.7 at 1000 A/m 2 for 2420 h 2 and subsequently, another electrolysis was carried out in 0.5 M NaCl solution of pH 8.7 at 1000 A/m 2 for 1000 Coulombs to determine chlorine evolution.
  • the oxygen evolution efficiency was calculated on the difference between the amount of charge passed and that of chlorine formation obtained by iodimetric titration. The results are shown in Table 2. It has been ascertained that the electrode of the present invention maintains high oxygen evolution efficiency for a long period of time in the electrolysis of the solution containing chloride ion. Table 2 No.

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  • 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)

Claims (1)

  1. Électrode d'évolution d'oxygène pour la production d'oxygène sans formation de chlore dans l'électrolyse de solutions aqueuses contenant des ions chlore, qui est préparée en déposant une couche intermédiaire et une couche d'électro-catalyseur dans cet ordre sur un substrat électriquement conducteur réalisé en titane ; dans laquelle la couche intermédiaire, qui est préparée par calcination,
    est constituée d'oxydes multiples d'un ou plusieurs éléments du groupe platine, Sn et Sb tels que le rapport cationique Sn/Sb est de 1 à 40, et dans laquelle la somme de Sn et Sb partage, en termes de cations, 90 % ou moins des oxydes multiples et le reste est l'oxyde de l'élément ou des éléments du groupe platine ; et
    dans laquelle les cations de la couche d'électro-catalyseur, qui est préparée par déposition anodique, sont constitués, en termes de cations, de 0,1 à 3 % de Sn, 0,2 à 20 % de Mo et/ou W, le reste de Mn.
EP07119704A 2007-10-31 2007-10-31 Électrode d'évolution de l'oxygène Ceased EP2055807B1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
DE602007007783T DE602007007783D1 (de) 2007-10-31 2007-10-31 Elektrode für Sauerstoffentwicklung
EP07119704A EP2055807B1 (fr) 2007-10-31 2007-10-31 Électrode d'évolution de l'oxygène

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
EP07119704A EP2055807B1 (fr) 2007-10-31 2007-10-31 Électrode d'évolution de l'oxygène

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EP2055807A1 EP2055807A1 (fr) 2009-05-06
EP2055807B1 true EP2055807B1 (fr) 2010-07-14

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EP3418429A1 (fr) * 2017-06-21 2018-12-26 Covestro Deutschland AG Électrode à diffusion de gaz destinée à réduire l'oxyde d'azote
CN113693954B (zh) * 2021-09-05 2024-02-20 诗乐氏实业（深圳）有限公司 一种抗菌洗手液

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GB1244650A (en) * 1968-10-18 1971-09-02 Ici Ltd Electrodes for electrochemical processes
US4028215A (en) * 1975-12-29 1977-06-07 Diamond Shamrock Corporation Manganese dioxide electrode
US4208450A (en) * 1975-12-29 1980-06-17 Diamond Shamrock Corporation Transition metal oxide electrodes

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EP2055807A1 (fr) 2009-05-06
DE602007007783D1 (de) 2010-08-26

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