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WO2005063393A1 - Procede permettant d'electrolyser de l'eau a l'aide d'un photocatalyseur organique - Google Patents

Procede permettant d'electrolyser de l'eau a l'aide d'un photocatalyseur organique Download PDF

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Publication number
WO2005063393A1
WO2005063393A1 PCT/JP2004/018886 JP2004018886W WO2005063393A1 WO 2005063393 A1 WO2005063393 A1 WO 2005063393A1 JP 2004018886 W JP2004018886 W JP 2004018886W WO 2005063393 A1 WO2005063393 A1 WO 2005063393A1
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Prior art keywords
electrode
organic semiconductor
type organic
water
electrolysis
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English (en)
Japanese (ja)
Inventor
Keiji Nagai
Toshiyuki Abe
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Kansai Technology Licensing Organization Co Ltd
TMT Machinery Inc
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Kansai Technology Licensing Organization Co Ltd
TMT Machinery Inc
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Priority to JP2005516568A priority Critical patent/JP3995051B2/ja
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • 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
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B1/00—Electrolytic production of inorganic compounds or non-metals
    • C25B1/01—Products
    • C25B1/02—Hydrogen or oxygen
    • C25B1/04—Hydrogen or oxygen by electrolysis of water
    • 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
    • C25B1/00—Electrolytic production of inorganic compounds or non-metals
    • C25B1/50—Processes
    • C25B1/55—Photoelectrolysis
    • 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

Definitions

  • the present invention relates to a method for efficiently electrolyzing water into hydrogen and oxygen under light irradiation using an organic photocatalyst activated by light, particularly visible light, as an electrode material.
  • a conventional alkaline water electrolyzer has been put to practical use under conditions requiring a high applied voltage of 1.7 to 2.0 V at a high temperature of about 60 to 80 ° C or higher (see Non-Patent Document 1). .
  • electrolysis of water requires the addition of excess thermal energy and an additional overvoltage of approximately 0.5-0.8 V with respect to the theoretical voltage of 1.23 V.
  • Non-Patent Document 2 reports a water decomposition reaction by an inorganic semiconductor photocatalyst using light energy.
  • the photocatalyst is only a few types of titanium oxide, composites thereof, tungsten oxide, and the like that can utilize ultraviolet light or near-ultraviolet visible light (Non-Patent Document 3 and the like), and covers the entire visible light region. There is no known photocatalyst capable of utilizing light over a wide range.
  • Non-Patent Document 5 describes a single-layer electrode using an organic semiconductor such as anthracene.
  • an organic semiconductor such as anthracene.
  • a sufficient photocurrent has not been obtained, and the performance of this organic material cannot be improved. It is stated that it is impossible to build a good photovoltaic cell and use it to extract chemical energy.
  • Patent Document 1 JP-A-9-234374
  • Non-Patent Document 1 Electrochemistry and Industrial Physical Chemistry April, p278-282, 2003
  • Non-Patent Document 2 Nature, 414, pp. 625-627 (2001)
  • Non-Patent Document 3 Chem. Commun., 150 (1992)
  • Non-Patent Document 4 J. Chem. Soc. Faraday Trans., 93, 221 (1997)
  • Non-Patent Document 5 Review of Chemistry No.45 Functional Organic Thin Film Published November 25, 1984
  • the present invention provides an electrode material using an organic photocatalyst capable of utilizing light in the ultraviolet and visible regions, and electrolyzes water under light irradiation to form hydrogen and hydrogen. It is a main object to provide a method for efficiently producing oxygen.
  • the present inventors have conducted intensive studies to achieve the above object, and as a result, irradiated an organic photocatalyst comprising a specific p-type organic semiconductor and a specific n-type organic semiconductor with ultraviolet light or visible light. Then, they found that a photocatalytic oxidation-reduction reaction occurs through unidirectional photo-induced electron transfer. Further, when electrolysis of water was performed using an electrode using the organic photocatalyst as an electrode material under irradiation of ultraviolet light or visible light, it was found that electrolysis was possible under milder conditions. The present inventors have further developed the present invention based on these findings.
  • the present invention provides the following organic photocatalyst, electrode material for electrolysis of water, and the electrode material And an electrolysis method for water using the electrode, a water electrolysis apparatus, and the like.
  • Item 1 An electrode material for water electrolysis comprising an organic photocatalyst containing a p-type organic semiconductor and an n-type organic semiconductor.
  • Item 2 The electrode material for electrolysis of water according to Item 1, wherein the p-type organic semiconductor is a macrocyclic ligand compound or a metal complex thereof.
  • Item 3 The electrode material for electrolysis of water according to Item 1 or 2, wherein the p-type organic semiconductor is at least one member selected from the group consisting of a phthalocyanine derivative, a naphthalocyanine derivative, and a porphyrin derivative.
  • Item 4 The electrode material for electrolysis of water according to Item 1, 2 or 3, wherein the n-type organic semiconductor is a polycyclic aromatic compound.
  • Item 5 The item in which the n-type organic semiconductor is at least one selected from the group consisting of fullerenes, carbon nanotubes, a conductive polymer doped with an electron donor, a perylene derivative, and a naphthalene derivative. 14. The electrode material for electrolysis of water according to any one of items 1-4.
  • Item 6 An electrode in which the surface of an electrode substrate is coated with the electrode material for water electrolysis according to any one of Items 115.
  • Item 7 The electrode according to item 6, wherein the surface of the electrode substrate is coated with a first layer made of an n-type organic semiconductor and a second layer made of a p-type organic semiconductor. An anode electrode that supports a transition metal catalyst on the second layer, if necessary.
  • Item 8 The electrode according to item 6, wherein the surface of the electrode substrate is coated with a first layer made of a p-type organic semiconductor and a second layer made of an n-type organic semiconductor.
  • a force sword electrode that supports a transition metal catalyst on the second layer, if necessary.
  • Item 9 The electrode according to item 6, wherein the electrode substrate is a conductive transparent glass substrate, a metal substrate, or a carbon-based substrate.
  • An electrolysis apparatus for water comprising: an anode electrode according to item 7, an electrode serving as a force source electrode according to item 8, a constant potential power supply, an aqueous electrolyte solution, and a light source.
  • Item 11 The item according to Item 10, wherein the anode electrode and the force source electrode are connected to a constant potential power supply, and the anode electrode and the force source electrode are immersed in an aqueous electrolyte solution. Water electrolysis equipment.
  • Item 12 The water electrolysis apparatus according to Item 11, wherein a voltage is applied to the anode electrode and the force source electrode with a constant potential power supply while irradiating the electrodes with light. Disassembly method.
  • Item 13 The water electrolysis method according to item 12, wherein the applied voltage is about 0.3 to 1.2 V.
  • Item 14 An electrode comprising the anode electrode and the force source electrode according to Item 7, or an electrode comprising the force electrode and the anode electrode according to Item 8, a constant potential power source, an aqueous electrolyte solution, and a light source. Water electrolysis equipment.
  • Item 15 The water electrolysis apparatus according to item 14, wherein the anode electrode and the force source electrode are connected to a constant potential power supply, and the anode electrode and the force source electrode are immersed in an aqueous electrolyte solution.
  • Item 16 The water electrolysis apparatus according to Item 15, wherein a voltage is applied to the anode electrode and the force source electrode with a constant potential power supply while irradiating the electrodes with light. Disassembly method.
  • Item 17 The water electrolysis method according to Item 16, wherein the applied voltage is about 1.0 to 1.4 V.
  • Item 18 The method for electrolyzing water according to Item 12 or 16, wherein the irradiation light is natural light.
  • Item 19 The water electrolysis method according to Item 12 or 16, wherein oxygen is generated from the anode electrode and hydrogen is generated from the force source electrode.
  • Item 20 An organic photocatalyst containing a p-type organic semiconductor and an n-type organic semiconductor.
  • Item 21 The organic photocatalyst according to item 20, wherein the p-type organic semiconductor is a macrocyclic ligand compound or a metal complex thereof.
  • Item 22 The organic photocatalyst according to item 20, wherein the p-type organic semiconductor is at least one member selected from the group consisting of a phthalocyanine derivative, a naphthalocyanine derivative, and a porphyrin derivative.
  • Item 23 The organic photocatalyst according to item 20, wherein the n-type organic semiconductor is a polycyclic aromatic compound.
  • Item 24 Item 20 wherein the n-type organic semiconductor is at least one selected from the group consisting of fullerenes, carbon nanotubes, a conductive polymer doped with an electron donor, a perylene derivative, and a naphthalene derivative.
  • the organic photocatalyst according to the above.
  • the present invention will be described in detail.
  • the organic photocatalyst of the present invention contains a p-type organic semiconductor and an n-type organic semiconductor, and is preferably used as an electrode material for water electrolysis described later because it is stable in a medium containing water.
  • P-type organic semiconductors include macrocyclic ligand compounds or metal complexes thereof.
  • the macrocyclic ligand compound means a cyclic compound that can be a ligand of a metal containing an atom having an unpaired electron on the ring, and the metal complex is a metal complex with the macrocyclic ligand. It means a metal complex consisting of metal atoms. Examples of the atom having an unpaired electron include a nitrogen atom and an oxygen atom, and a nitrogen atom is preferable. Examples of the metal atom include metal elements belonging to groups 11 to 15 of the periodic table, preferably metal elements belonging to groups 4 to 14.
  • the metal complex is usually a metal complex composed of the metal atom and the macrocyclic ligand compound in a molar ratio of 1: 1 to form a four-coordinate planar complex.
  • macrocyclic ligand compound or its metal complex examples include a phthalocyanine derivative, a naphthalocyanine derivative, and a porphyrin derivative.
  • the phthalocyanine derivative means a compound having a basic skeleton of phthalocyanine.
  • M 1 represents a metal atom selected from the group consisting of Groups 414 of the Periodic Table or an atomic group containing the metal atom, and a dotted line represents a coordination bond.
  • the atomic group containing the metal atom means a group in which another ligand (eg, oxygen or cyano group) is coordinated with the metal (for example, Ti- ⁇ ).
  • M 1 is Co, Pt,
  • Phthalocyanine derivatives which are Os, Mn, Ir, Fe, Rh, Cu, Zn, Ni, Pd or Ru are preferred, and cobalt phthalocyanine is particularly preferred in terms of the amount of oxygen generated in the electrolysis of water. All of these compounds are commercially available or can be easily produced by those skilled in the art.
  • the naphthalocyanine derivative means a compound having a basic skeleton of naphthalocyanine. Specifically, for example, the following formula (2A) or (2B):
  • M 2 represents a metal atom selected from the group consisting of Groups 414 of the Periodic Table or an atomic group containing the metal atom, and a dotted line represents a coordination bond.
  • one of the periodic table 4 one 14 metal atom shown by M 2, Group 4 (especially, ⁇ ), Group 5 (in particular, V), Group 6 (in particular, Mo), 7 group ( In particular, Mn), Group 8 (Fe, Ru, Os), Group 9 (Co, Rh, Ir), Group 10 (Ni, Pd, Pt), Group 11 (particularly Cu), Group 12 (particularly Zn) , Group 13 (especially Al), group 14 (especially Pb ).
  • the atomic group containing the metal atom means one in which another ligand (for example, oxygen or cyano group) is coordinated to the metal (for example, Ti-O).
  • M 2 is Co, Pt,
  • Naphthalocyanine derivatives which are ⁇ s, Mn, Ir, Fe, Rh, Cu, Zn, Ni, Pd or Ru are preferred, and cobalt naphthalocyanine is particularly preferred in terms of the amount of oxygen generated in the electrolysis of water. These compounds are all commercially available or can be easily prepared by those skilled in the art.
  • the porphyrin derivative means a compound having a basic skeleton of porphyrin. Specifically, for example, the following formula (3A) or (3B):
  • R 3 represents a hydrogen atom, an alkyl group, an aryl group or a heteroaryl group
  • M 3 contains a metal atom selected from the group consisting of Groups 4 to 14 of the periodic table or a metal atom thereof (Indicates atomic groups, dotted lines indicate coordination bonds.)
  • the alkyl group represented by R 3 above is a C straight-chain or branched-chain alkyl.
  • N-propyl isopropyl, n-butyl, sec-butyl, isobutyl, n-pentyl, n-hexyl, n-heptyl, n-octyl and the like.
  • Examples of the aryl group represented by R 3 include a monocyclic or bicyclic aryl group, and specific examples include phenyl and naphthyl.
  • the atomic group containing the metal atom means a group in which another ligand (eg, oxygen or cyano group) is coordinated with the metal (for example, Ti- ⁇ ).
  • These compounds are all commercially available or can be easily produced by those skilled in the art.
  • the n-type organic semiconductor includes a polycyclic aromatic compound (which may be partially saturated).
  • a polycyclic aromatic compound is a compound having a structure in which at least two or more aromatic rings are fused, or a structure in which multiple aromatic rings are bonded via an unsaturated bond (double bond, triple bond, etc.).
  • the aromatic ring includes, in addition to the benzene ring and the like, a heteroaromatic ring such as a pyrrole ring, an imidazole ring, a pyridine ring and a quinoxaline ring. ,).
  • the polycyclic aromatic compound may have various substituents as long as the compound does not adversely affect the present invention.
  • substituents include an electron withdrawing group, and specific examples include a carbonyl group, a sulfone group, and a sulfoxide group.
  • polycyclic aromatic compound examples include fullerenes such as C60, C70, C76, C82, and C84; carbon nanotubes; and electron donors (phenylenediamine, tetraaminoethylene, tris (2, Conductive polymers (polyimide, polyphenylenevinylene, polyparaphenylene, polypyrrole, etc.) doped with 2-biviridine) ruthenium; perylene derivatives; naphthalene derivatives. Among them, perylene derivatives, naphthalene derivatives, fullerenes (C60 and the like) and the like are preferably employed, and perylene derivatives and fullerenes (C60 and the like) are particularly preferable.
  • fullerenes such as C60, C70, C76, C82, and C84
  • carbon nanotubes such as C60, C70, C76, C82, and C84
  • electron donors phenylenediamine, tetraaminoethylene, tris
  • the perylene derivative means a compound having a basic skeleton of perylene.
  • R 1 represents an alkyl group or an aryl group
  • the naphthalene derivative means a compound having a basic skeleton of naphthalene. Specifically, for example, the following formula (5A):
  • R 2 represents an alkyl group or an aryl group
  • the alkyl group represented by R 1 or R 2 above is a C straight-chain or branched-chain And an alkyl group of C 2 is preferable. Specifically, methyl
  • Ariru group represented by R 1 or R 2 include Ariru group mono- or bicyclic, in particular phenyl, naphthyl and the like.
  • the organic photocatalyst of the present invention there is no particular limitation on the form of bonding between the p-type organic semiconductor and the n-type organic semiconductor, but it is preferable to bond them so that the contact area between them increases.
  • a film-shaped p-type organic semiconductor and an n-type organic semiconductor may be joined, or one of the organic semiconductor films may be coated with the other organic semiconductor component to have a layer (film) structure.
  • water is efficiently converted into hydrogen and oxygen by applying a voltage while irradiating light to an electrode coated with an organic photocatalyst comprising a p-type organic semiconductor and an n-type organic semiconductor. It is characterized by electrolysis. A schematic diagram is shown in FIG.
  • the electrode used in the electrolysis of water of the present invention has an electrode substrate surface coated with an organic photocatalyst.
  • Examples of the electrode substrate include a conductive transparent glass substrate, a metal substrate, and a carbon-based substrate.
  • a conductive transparent glass base material coated with indium tin oxide (ITO) or the like; a metal base material such as platinum; a carbon base material such as graphite, diamond, glassy carbon or the like can be used.
  • the resistance value of the electrode substrate is, for example, 5-100 ⁇ m 2 , preferably 820 ⁇ m 2 .
  • the shape of the electrode substrate be a variety of shapes. A force that can be used.
  • the organic photocatalyst covering the electrode substrate is composed of a specific p-type organic semiconductor and a specific n-type organic semiconductor.
  • a p-type organic semiconductor having a high activity as an oxygen generation catalyst capable of efficiently generating oxygen in the electrolysis of water during light irradiation is used. It is.
  • the p-type organic semiconductor include the above-described macrocyclic ligand compounds and metal complexes thereof, and preferably include phthalocyanine derivatives, naphthalocyanine derivatives, and porphyrin derivatives. More preferably, compounds represented by the formulas (1A), (IB) ⁇ (2A), (2B), (3A), and (3B) are preferable.
  • a metal complex of phthalocyanine (cobalt phthalocyanine) in which M 1 is represented by Co in the formula (1B) is preferable.
  • the above-mentioned p-type organic semiconductor is available as a commercial product or can be easily manufactured by those skilled in the art.
  • the n-type organic semiconductor used for the electrode of the present invention can generate hydrogen efficiently in the electrolysis of water during light irradiation, and has a favorable relationship with the p-type organic semiconductor. Those having a pn junction relationship are used.
  • the n-type organic semiconductor include the above-mentioned polycyclic aromatic compounds (which may be partially saturated), and preferably include perylene derivatives, naphthalene derivatives, and fullerenes. More preferably, compounds represented by formulas (4A), (4B), (4C), and (5A) are preferable.
  • perylene derivatives (3,4,9,10-perylenetetracarboxyl-bisbenzimidazole) or fullerenes (C60 and the like) represented by the formula (4A) are preferably used.
  • n-type organic semiconductor is available as a commercial product or can be easily manufactured by those skilled in the art.
  • the electrode of the present invention is formed by coating an electrode substrate with an organic photocatalyst obtained by combining the n-type organic semiconductor and the p-type organic semiconductor.
  • the specific configuration of the electrode is as follows.
  • the anode has a first layer (film) made of an n-type organic semiconductor on the surface of an electrode substrate, and has a second layer (film) made of a p-type organic semiconductor thereon.
  • the first layer is a continuous film having a thickness of usually about 200 to 800 nm (preferably about 250 to 650 nm) covering the electrode, and the second layer is usually about 20 to 500 nm (preferably 30 to 350 nm) covering the electrode. )).
  • the first layer is more preferably about 250 to 650 nm, and the second layer is more preferably about 30 350 nm.
  • a second layer Transition metal on A catalyst eg, a Ni, Pd, Pt, Ir catalyst or the like, preferably a Pt or Ir catalyst
  • the transition metal catalyst supported on the second layer does not need to completely cover the second layer and may be dispersed and supported.
  • the transition metal catalyst is supported on the second layer in the form of fine particles having an average particle size of about 5 to 800 nm (preferably about 10 100 nm).
  • the anode electrode employing such a configuration becomes an efficient oxygen generating electrode.
  • electrons excited by light especially visible light
  • holes generated by photoexcitation flow through the p-type organic semiconductor toward the electrolyte.
  • water or hydroxide ions
  • the force source electrode has a first layer (film) made of a p-type organic semiconductor on the surface of an electrode substrate, and a second layer (film) made of an n-type organic semiconductor thereon.
  • the first layer is a continuous film having a thickness of usually about 20 to 500 nm (preferably about 30 to 350 nm) covering the electrode, and the second layer is generally about 200 to 800 nm (about 200 to 800 nm) covering the first layer. It preferably consists of a continuous film having a thickness of about 250 to 650.
  • the first layer is more preferably about 30 to 350 nm
  • the second layer is more preferably about 250 650 nm.
  • a force source electrode A transition metal catalyst (eg, a Ni, Pd, Pt, Ir catalyst or the like, preferably a Pt or Ir catalyst) supported on the layer may be used.
  • the transition metal catalyst supported on the second layer does not need to completely cover the second layer and may be dispersed and supported.
  • a transition metal catalyst has an average particle size of 5800 nm. Particles (preferably about 10-100 nm) are supported on the second layer.
  • the cathode electrode employing such a configuration becomes an efficient hydrogen generating electrode.
  • a force source electrode electrons excited by light (especially visible light) flow in the n-type organic semiconductor toward the electrolyte, and holes generated by photoexcitation flow in the p-type organic semiconductor toward the electrode substrate.
  • water or protons receives electrons and is reduced to generate hydrogen (see, for example, Figure 1).
  • each electrode substrate As a method of coating each electrode substrate with an n-type organic semiconductor and a p-type organic semiconductor, known methods can be adopted, for example, vacuum deposition, sputtering, electrochemical coating (electrodeposition). ) And coating from a solution. Above all, with respect to the perylene derivative Z phthalocyanine derivative system, a vacuum deposition method is preferable because a uniform coating film can be obtained. It is preferable that the thickness of each organic semiconductor covering each electrode is appropriately set in the above-described range.
  • the anode electrode forms an n-type organic semiconductor layer (first layer) by vacuum-depositing an n-type organic semiconductor on a conductive transparent glass substrate, and forms a p-type organic semiconductor thereon.
  • the P-type organic semiconductor layer (second layer) may be formed by vacuum evaporation.
  • the force source electrode is formed by vacuum-depositing a P-type organic semiconductor on a conductive transparent glass substrate to form a P-type organic semiconductor layer (first layer), and then vacuum-depositing an n-type organic semiconductor thereon.
  • the organic semiconductor layer (second layer) may be formed.
  • a known method such as an electroanalysis method (electrochemical reduction) can be employed.
  • an electroanalysis method electrochemical reduction
  • platinum salts such as KPtCl, KPtCl, and HPPtCl
  • the applied voltage is about 0-0.2 V (vs. Ag / AgCl).
  • the concentration of the acid is usually about ImMlOmM, and the concentration of the platinum salt is preferably about O.lmM ImM.
  • An electrode coated with force, and thus with the organic photocatalyst of the present invention, is produced.
  • water especially light in the entire visible wavelength range
  • hydrogen and oxygen can be efficiently used.
  • the electrode using the organic photocatalyst of the present invention has a feature that the electrode itself is stable without being decomposed by oxidation or the like even under the condition of electrolysis of water.
  • a force source electrode and / or an anode electrode containing the above-mentioned organic photocatalyst are used.
  • a force source electrode having a first layer made of a p-type organic semiconductor and a second layer made of an n-type organic semiconductor on the surface of an electrode substrate, and an n-type organic semiconductor
  • an anode electrode having a first layer comprising a P-type organic semiconductor and a second layer comprising a P-type organic semiconductor
  • a first layer comprising a P-type organic semiconductor and a second layer comprising an n-type organic semiconductor on the surface of the electrode substrate A combination of a force source electrode having a transition metal catalyst and an anode electrode having a first layer made of an n-type organic semiconductor and a second layer made of a p-type organic semiconductor on the surface of the electrode substrate
  • an electrode substrate Force electrode having a first layer made of a p-type organic semiconductor and a second layer made of an n-type organic semiconductor on the surface of the electrode, and a first layer made of an n-type organic semiconductor and a p-type organic semiconductor on the surface of the electrode, and a first
  • a combination of the above-mentioned force electrode or anode electrode containing an organic photocatalyst and an anode or force electrode consisting of a known electrode such as a platinum electrode
  • a known electrode such as a platinum electrode
  • one of the electrodes may be an electrode containing the organic photocatalyst of the present invention, and the other may be a known electrode.
  • aqueous electrolyte solution used in the electrolysis of the present invention an acidic aqueous solution or an alkaline aqueous solution is suitably used.
  • the acidic aqueous solution is preferably an aqueous solution containing an acid such as phosphoric acid or sulfuric acid. Especially preferred Alternatively, it is a phosphoric acid aqueous solution.
  • the concentration of the acid in the aqueous solution may usually be about 1 mM to 1 M.
  • the pH of the acid aqueous solution is preferably about 113.
  • Examples of the alkaline aqueous solution include an aqueous solution of an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide, which contains an electrolyte such as a phosphate, a sulfate, a nitrate, a carbonate, or an acetate. preferable. Particularly preferred is an aqueous solution of an alkali metal hydroxide.
  • concentration of the alkali metal hydroxide in the aqueous solution may usually be about 1 mM 1 M.
  • the pH of an aqueous alkali metal hydroxide solution is preferably about 10-11.
  • the light used in the present invention can use light having a wide range of wavelengths (wavelength of about 220 to 800 nm).
  • the light source is selected from, for example, natural light (sunlight), fluorescent lamp, halogen lamp, high-pressure mercury lamp, low-pressure mercury lamp, black light, excimer laser, deuterium lamp, xenon lamp, Hg-Zn-Pb lamp, etc.
  • Different types of light sources or two types of light sources having different wavelength ranges can be used.
  • the present invention is extremely practical in that natural light can be used for electrolysis over almost the entire wavelength range (wavelength 300-800 ⁇ m) due to the nature of the organic photocatalyst comprising an n-type organic semiconductor and a p-type organic semiconductor. .
  • the light source may be usually irradiated with light from the light source to an anode electrode containing an organic photocatalyst and / or a force sword electrode containing an organic photocatalyst.
  • anode electrode containing an organic photocatalyst and / or a force sword electrode containing an organic photocatalyst.
  • the electrode containing the organic photocatalyst may be irradiated.
  • an anode electrode containing an organic photocatalyst and a force sword electrode containing an organic photocatalyst were used, and when light was applied to both electrodes, the applied voltage of the power source was 0.3 to 1.2 V A low voltage (preferably about 0.8 1. IV) is sufficient.
  • the present invention employs an electrode using an organic photocatalyst as described above, so that a light-induced voltage is generated by light irradiation, and a power supply having a lower voltage than the theoretical voltage can be used. is there. In other words, by effectively using light energy, the power consumption for electrolysis can be increased. The ability to reduce S can.
  • the applied voltage of the power supply is At a low voltage of about 1.0 1.4V (preferably about 1.1 to 1.3V). Also in this case, by using light energy at the electrode including the organic photocatalyst, the applied voltage can be reduced and the power consumption used for the electrolysis can be significantly reduced.
  • the method for decomposing water of the present invention it is possible to effectively utilize solar energy and to generate oxygen and hydrogen safely and efficiently. Further, the electrolysis of water of the present invention can be carried out at normal temperature (for example, about 0.degree. C.), which is advantageous in that heating and pressurization are not required.
  • the generated hydrogen can be used effectively for fuel cell fuels and existing hydrogen utilization technologies (eg, petroleum refining, petrochemical manufacturing, metallurgy, etc.).
  • the water electrolysis apparatus of the present invention includes the above-described anode electrode, force electrode, power supply (constant potential power supply), electrolyte aqueous solution, and light source (for example, see FIG. 1).
  • the anode electrode and the force source electrode are connected to a power supply for applying a voltage, and each electrode is partially or entirely immersed in an aqueous electrolyte solution.
  • an electrolyzer having a single-chamber bipolar cell is exemplified.
  • the anode electrode and the force sword electrode those described above are used.
  • the aqueous electrolyte solution those described above are used.
  • the pH is preferably about 113, and in the case of an electrode coated with a perylene derivative / phthalocyanine derivative, the pH is preferably about 10-11.
  • the pH of the electrolyte solution in which the anode electrode and the force electrode are immersed may be different.
  • a reaction cell with a salt bridge separating the electrolyte solution of the anode electrode and the force electrode is used.
  • the embodiment of Example 6 is exemplified.
  • the reaction tank on the anode electrode (anode) side is alkali water adjusted to pH-11 with sodium hydroxide or potassium hydroxide, and the reaction on the power source electrode (cathode) side.
  • Acidified tank adjusted to pH-2 with phosphoric acid or sulfuric acid There is a bipolar cell that uses water and connects both tanks with a salt bridge.
  • an organic photocatalyst capable of utilizing light in the ultraviolet and visible regions is used as an electrode material, and water is efficiently converted into hydrogen and oxygen under mild conditions under light irradiation.
  • the angle of separation can be S.
  • the present invention provides a method for electrolysis of clean water (including hydrogen ions and hydroxide ions) that can effectively utilize natural energy (solar energy) and reduce carbon dioxide emissions. .
  • FIG. 1 is a schematic view of a method for electrolyzing water using an organic photocatalyst of the present invention.
  • FIG. 2 is a schematic diagram of a photoelectrochemical measurement device according to Examples 1 and 2 and Comparative Example 1.
  • FIG. 3 is a schematic diagram of a photoelectrochemical measurement device according to Examples 3 and 4 and Comparative Examples 2 and 3.
  • FIG. 4 is a schematic diagram of a photoelectrochemical measurement device according to Example 5.
  • FIG. 5 is a schematic diagram of a photoelectrochemical measurement device according to Example 6.
  • FIG. 6 is a schematic diagram of a photoelectrochemical measurement device according to Example 7.
  • Example 1 (Oxygen-causing vortex at irradiation of halogen lamp) Electrode substrate / PV / CoPc is used as photoanode (working electrode), platinum wire as counter electrode, silver / silver chloride electrode as reference electrode, and alkaline water adjusted to pH-11 with sodium hydroxide or potassium hydroxide. Thus, a three-electrode cell as shown in FIG. 2 was constructed. When electrolysis was carried out under the halogen lamp irradiation at an applied potential of +0.3 V, oxygen was generated at about 3-4 ⁇ 1 / h. The specific operation procedure is shown below.
  • n-type semiconductor 3,4,9,10-perylenetetracarboxynor-bisbenzimidazole (hereinafter referred to as “PV”) and p-type semiconductor cobalt lid Mouth cyanine (hereinafter referred to as “CoPc”) was used.
  • PV 3,4,9,10-perylenetetracarboxynor-bisbenzimidazole
  • CoPc p-type semiconductor cobalt lid Mouth cyanine
  • the production of the organic photocatalytic device was performed by a vacuum evaporation method.
  • a conductive transparent glass substrate hereinafter referred to as “ITO-coated glass substrate” coated with indium monotin oxide (ITO) (manufactured by Nippon Sheet Glass Co., Ltd., resistance 13 ⁇ cm- 2 ; transmittance of glass 85%;
  • ITO indium monotin oxide
  • the PV was laminated with a thickness of 250 to 650 nm on the indium tin oxide laminate thickness of 110 nm, and then the CoPc was laminated with a thickness of 30 to 350 nm on the PV.
  • a portion corresponding to X 0.5 cm was wiped off with acetone, and a conductive wire was attached using a silver-containing epoxy adhesive (T-700, manufactured by Toyo Ink Manufacturing Co., Ltd.).
  • T-700 manufactured by Toyo Ink Manufacturing Co., Ltd.
  • the electrode was insulated with an epoxy adhesive to form an organic photocatalyst-coated electrode.
  • the photocatalytic reaction cell was produced by the following method. Using the organic photocatalyst-coated electrode prepared in (3) above as the working electrode, a platinum wire as the counter electrode, and a silver / silver chloride electrode (the internal solution is a saturated aqueous solution of potassium chloride) as a reference electrode, constructing a one-chamber type three-electrode cell. did. As the electrolyte solution, alkaline water adjusted to pH 11 with sodium hydroxide or potassium hydroxide was used.
  • Example 2 (light, cattle in fr s temple.
  • a three-electrode cell as shown in FIG. 2 was constructed.
  • electrolysis was performed under an applied potential of +0.4 V under natural light irradiation, about 1.5 uL / h of oxygen and about 3.5 ⁇ 1 / h of hydrogen were generated.
  • the specific operation procedure is shown below.
  • PV as an n-type semiconductor
  • CoPc as a p-type semiconductor
  • those purified by sublimation were used.
  • PV is 250-300 nm thick, then CoPc on PV was laminated at a thickness of 135-145 nm.
  • a portion corresponding to X 0.5 cm was wiped off with acetone, and a conductive wire was attached using a silver-containing epoxy adhesive (T-700, manufactured by Toyo Ink Manufacturing Co., Ltd.).
  • T-700 manufactured by Toyo Ink Manufacturing Co., Ltd.
  • the electrode was insulated with an epoxy adhesive to form an organic photocatalyst-coated electrode.
  • the photocatalytic reaction cell was produced by the following method. Using the organic photocatalyst-coated electrode prepared in (3) above as the working electrode, a platinum wire as the counter electrode, and a silver / silver chloride electrode (the internal solution is a saturated aqueous solution of potassium chloride) as a reference electrode, constructing a one-chamber type three-electrode cell. did. As the electrolyte solution, alkaline water adjusted to pH-11 with sodium hydroxide or potassium hydroxide was used.
  • an electrode supporting a working oxygen generating catalyst was prepared, and electrocatalytic oxygen in alkaline water adjusted to pH-11 with sodium hydroxide or potassium hydroxide was used. Occurred.
  • the oxygen generating catalyst Ir ⁇ , whose high catalytic activity is known, was used. The specific operation procedure is shown below.
  • Oxygen generation of 5-6 ⁇ 1 / h- 1 was confirmed.
  • PV as an n-type semiconductor and phthalocyanine as a p-type semiconductor (hereinafter referred to as “H Pc”) were used as organic photocatalyst materials.
  • H Pc phthalocyanine as a p-type semiconductor
  • a portion corresponding to X 0.5 cm was wiped off with acetone, and a conductive wire was attached using a silver-containing epoxy adhesive (T-700, manufactured by Toyo Ink Manufacturing Co., Ltd.).
  • T-700 manufactured by Toyo Ink Manufacturing Co., Ltd.
  • the electrode was insulated with an epoxy adhesive to form an organic photocatalyst-coated electrode.
  • the photocatalytic reaction cell was produced by the following method. Using the organic photocatalyst-coated electrode prepared in (3) above as the working electrode, a platinum wire as the counter electrode, and a silver / silver chloride electrode (the internal solution is a saturated aqueous solution of potassium chloride) as a reference electrode, constructing a one-chamber type three-electrode cell. did. As the electrolyte solution, alkaline water adjusted to pH 11 with sodium hydroxide or potassium hydroxide was used.
  • Example 3 an electrode supporting a hydrogen generating catalyst that works for a long time was produced, and hydrogen was generated in alkaline water adjusted to pH-11 with sodium hydroxide or potassium hydroxide. Platinum black, which is known to have high activity, was used as the hydrogen generation catalyst. The specific operation procedure is shown below.
  • the electrode (about 0.2cm 2 ) is subjected to force sword polarization, and about 3-4 coulombs (C) are energized to become white. A gold black electrode was obtained. After washing this platinum black electrode with water, it was used for a hydrogen generation experiment.
  • Example 3 employing a force sword electrode containing an organic photocatalyst, a light power sword electrode was generated by irradiation with visible light, which was higher than Comparative Example 2 at a (noble) applied potential. Generation of hydrogen was confirmed.
  • C as an n-type semiconductor and H Pc as a p-type semiconductor were used.
  • H Pc as a p-type semiconductor
  • those purified by sublimation were used.
  • a portion corresponding to X 0.5 cm was wiped off with acetone, and a conductive wire was attached using a silver-containing epoxy adhesive (T-700, manufactured by Toyo Ink Manufacturing Co., Ltd.).
  • T-700 manufactured by Toyo Ink Manufacturing Co., Ltd.
  • the electrode was insulated with an epoxy adhesive to form an organic photocatalyst-coated electrode.
  • the photocatalytic reaction cell was produced by the following method. Using the organic photocatalyst-coated electrode prepared in (3) above as the working electrode, a platinum wire as the counter electrode, and a silver / silver chloride electrode (the internal solution is a saturated aqueous solution of potassium chloride) as a reference electrode, constructing a one-chamber type three-electrode cell. did. As an electrolyte solution, acidic water adjusted to pH 2 with phosphoric acid or sulfuric acid was used.
  • Example 4 an electrode supporting a hydrogen generating catalyst that works for a long time was prepared, and hydrogen was generated in acidic water adjusted to pH-2 with phosphoric acid or sulfuric acid. Platinum black, which is known to have high activity, was used as the hydrogen generation catalyst. The specific operation procedure is shown below.
  • ITO-coated glass substrate by law (manufactured by Asahi Glass Company, resistance 8 Omega cm- 2; transmittance of 85 percent glass; Injiu Musuzuokishido laminate thickness 174 nm) of the electrode (about lcm 2) to force cathode polarization, about 0.01 0.05 Coo Ron (C) was energized to obtain a platinum black electrode. After washing this platinum black electrode with water, it was used for a hydrogen generation experiment.
  • Example 4 employing a force sword electrode containing an organic photocatalyst, a light power sword current was generated by irradiation with visible light, and hydrogen was applied at a higher (noble) applied potential than Comparative Example 3. Occurrence was confirmed.
  • Example 5 (Existence of n solution using n hornworm shrinkage) Electrode substrate / PV / CoPc photo-anode electrode (anode), Electrode substrate / H Pc / PV / Platinum catalyst light
  • a bipolar cell as shown in Fig. 4 was constructed using alkaline water adjusted to pH-11 with sodium hydroxide or potassium hydroxide as the force source electrode (cathode).
  • oxygen was generated at about 3.5 ⁇ ⁇ / hydrogen at about 8.0 x l / h.
  • the specific operation procedure is shown below.
  • PV as an n-type semiconductor and CoPc or HPc as a p-type semiconductor were used.
  • PV, H Pc and CoPc were each purified by sublimation.
  • the production of the organic photocatalytic device was performed by a vacuum evaporation method.
  • PV was laminated with a thickness of 650 nm on an IT ⁇ -coated glass substrate (manufactured by Nippon Sheet Glass Co., Ltd., resistance 10 ⁇ cm- 2 ), and then CoPc was laminated with a thickness of 190 nm on the PV. Then it was cut into lcm x 1.5cm.
  • HPc was deposited on a thermally decomposable graphite with a cross-sectional area of lcm x 1.5cm at a thickness of 190 nm and PV was applied.
  • the layers were stacked to a thickness of 650 marauders, and further carried platinum black.
  • the photocatalytic reaction cell was produced by the following method.
  • a single-chamber bipolar cell was constructed using the organic photocatalyst-coated electrode prepared in (3) above as both electrodes.
  • the cell also has a function as a reference electrode due to the cell configuration.
  • Alkaline water adjusted to pH-11 with sodium hydroxide or potassium hydroxide was used as the electrolyte solution.
  • Example 5 in the electrolysis of water employing an anode electrode and an organic sword electrode containing an organic photocatalyst, a photo-induced electrode is generated by irradiation with visible light, and hydrogen and oxygen are generated at an applied voltage (0.9 V) lower than the theoretical voltage. Occurrence was confirmed.
  • Example 6 (Existence of n solution using shrunken hornworm)
  • the electrode substrate / PV / CoPc is the anode electrode (anode), and the electrode substrate / H Pc / C is the force electrode (negative electrode).
  • a bipolar cell as shown in Fig. 5 was constructed.
  • electrolysis was performed at an applied voltage of 0.9 V, about 3.0 ⁇ / h of oxygen and about 6.0 ⁇ / h of hydrogen were generated.
  • the specific operation procedure is shown below.
  • CoPc or HPc was used. PV, H Pc and CoPc were each purified by sublimation.
  • the production of the organic photocatalytic device was performed by a vacuum evaporation method.
  • PV was coated on an ITO-coated glass substrate (Nippon Sheet Glass Co., Ltd., resistance 13 ⁇ cm- 2 ; glass transmittance 85%; indium tin oxide laminated thickness 110 nm) with a thickness of 650 nm, and then PV On top, CoPc was laminated with a thickness of 190 nm. Then it was cut into lcm x 1.5cm.
  • the cathode as in the case of the anode, HPc is laminated on ITO at a thickness of 60 nm, C is laminated at a thickness of 120 nm, and platinum black is further supported.
  • the photocatalytic reaction cell was produced by the following method.
  • a bipolar cell was constructed using the organic photocatalyst-coated electrode prepared in (3) above as both electrodes.
  • For the electrolyte solution use alkaline water adjusted to pH-11 with sodium hydroxide or potassium hydroxide in the reaction tank on the anode side, and acidic water adjusted to pH 2 with phosphoric acid or sulfuric acid in the reaction tank on the cathode side, respectively.
  • both tanks were connected by a salt bridge, and the tank was used as a reaction cell.
  • the organic photocatalytic reaction was carried out using a measuring device as shown in FIG. Function generator (Hokuto Denko, HB-104), Coulomb meter (Hokuto Denko, HF-201) and XY recorder (Graphtec, WX-4000) equipped with a potentiometer / galvanostat (Hokuto Denko, HA-301), and a halogen lamp (150 W) was used as a light source.
  • the product was analyzed using a gas chromatograph (GC-8A, manufactured by Shimadzu Corporation).
  • Example 6 in the electrolysis of water using an anode electrode and a force source electrode containing an organic photocatalyst, a light-induced current is generated by irradiation with visible light, and hydrogen is applied at an applied voltage (0.9 V) lower than the theoretical voltage. Generation of oxygen was confirmed.
  • Example 7 yes n horned anode, t-solution using shrinkage
  • Electrode substrate / PV / CoPc is used as an anode electrode (anode), and a platinum rod is used as a force source electrode (cathode) using alkaline water adjusted to pH-11 with sodium hydroxide or potassium hydroxide as shown in Fig. 6.
  • a bipolar cell was constructed. When electrolysis was performed at an applied voltage of 1.1 V, about 3.5 ⁇ ⁇ / h of oxygen and about 8.0 ⁇ / h of hydrogen were generated. The specific operation procedure is shown below.
  • PV as an n-type semiconductor
  • CoPc as a p-type semiconductor
  • the production of the organic photocatalytic device was performed by a vacuum evaporation method.
  • the anode PV was laminated with a thickness of 650 nm on an ITO-coated glass substrate (manufactured by Nippon Sheet Glass Co., Ltd., resistance 10 ⁇ cm- 2 ), and then CoPc was laminated with a thickness of 190 nm on the PV. Then it was cut into lcm x 1.5cm. A white gold bar was used as the cathode.
  • the photocatalytic reaction cell was produced by the following method. Using the organic photocatalyst-coated electrode prepared in (3) above as an anode and a platinum rod as a cathode, a single-chamber bipolar cell was constructed. In this case, the cell Has a function as a reference electrode. As the electrolyte solution, alkaline water adjusted to pH-11 with sodium hydroxide or potassium hydroxide was used.

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Abstract

Cette invention concerne un procédé permettant de produire efficacement de l'hydrogène et de l'oxygène en électrolysant de l'eau au moyen d'un rayonnement de lumière, lequel procédé fait appel à un photocatalyseur organique capable d'utiliser efficacement toute la lumière se trouvant dans le visible. Cette invention concerne également un photocatalyseur organique contenant un semi-conducteur organique de type p et un semi-conducteur organique de type n, un matériau d'électrode pour électrolyse de l'eau composé d'un tel photocatalyseur organique, une électrode recouverte d'un tel matériau d'électrode, un procédé permettant d'électrolyser de l'eau à l'aide d'une telle électrode, un appareil permettant d'électrolyser de l'eau et analogue.
PCT/JP2004/018886 2003-12-26 2004-12-17 Procede permettant d'electrolyser de l'eau a l'aide d'un photocatalyseur organique Ceased WO2005063393A1 (fr)

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JP2009125609A (ja) * 2007-11-20 2009-06-11 National Institute Of Advanced Industrial & Technology シュウ酸類の電気化学的酸化反応用触媒
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CN111085107A (zh) * 2019-11-25 2020-05-01 苏交科集团股份有限公司 多孔沥青路面负载复合改性光催化剂净化车辆尾气的方法
JP2021194555A (ja) * 2020-06-09 2021-12-27 国立大学法人弘前大学 触媒電極、その製造方法およびそれを用いたギ酸酸化方法
JP7399423B2 (ja) 2020-06-09 2023-12-18 国立大学法人弘前大学 触媒電極、その製造方法およびそれを用いたギ酸酸化方法
WO2025047802A1 (fr) * 2023-08-31 2025-03-06 花王株式会社 Photocatalyseur à jonction

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