EP4394084A2 - Photokatalytische vorrichtung - Google Patents

Photokatalytische vorrichtung Download PDF

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Publication number
EP4394084A2
EP4394084A2 EP23203871.1A EP23203871A EP4394084A2 EP 4394084 A2 EP4394084 A2 EP 4394084A2 EP 23203871 A EP23203871 A EP 23203871A EP 4394084 A2 EP4394084 A2 EP 4394084A2
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EP
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Prior art keywords
electrode
layer
photocatalytic
light
power generation
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EP23203871.1A
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English (en)
French (fr)
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EP4394084A3 (de
Inventor
Hiromasa Takahashi
Naoto Fukatani
Daiko Takamatsu
Shin Yabuuchi
Jun Hayakawa
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Hitachi Ltd
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Hitachi Ltd
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Publication of EP4394084A3 publication Critical patent/EP4394084A3/de
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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
    • 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
    • C25B9/00—Cells or assemblies of cells; Constructional parts of cells; Assemblies of constructional parts, e.g. electrode-diaphragm assemblies; Process-related cell features
    • C25B9/50—Cells or assemblies of cells comprising photoelectrodes; Assemblies of constructional parts thereof
    • 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
    • C25B1/23—Carbon monoxide or syngas
    • 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
    • C25B11/052—Electrodes comprising one or more electrocatalytic coatings on a substrate
    • 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
    • C25B15/00—Operating or servicing cells
    • C25B15/08—Supplying or removing reactants or electrolytes; Regeneration of electrolytes
    • 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
    • C25B3/00—Electrolytic production of organic compounds
    • C25B3/01—Products
    • C25B3/07—Oxygen containing compounds
    • 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
    • C25B3/00—Electrolytic production of organic compounds
    • C25B3/20—Processes
    • C25B3/25—Reduction
    • C25B3/26—Reduction of carbon dioxide
    • 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
    • C25B9/00—Cells or assemblies of cells; Constructional parts of cells; Assemblies of constructional parts, e.g. electrode-diaphragm assemblies; Process-related cell features
    • C25B9/17—Cells comprising dimensionally-stable non-movable electrodes; Assemblies of constructional parts thereof
    • C25B9/19—Cells comprising dimensionally-stable non-movable electrodes; Assemblies of constructional parts thereof with diaphragms

Definitions

  • photovoltaic action allows electrons and holes to be separately extracted at electrodes. This can be used for an electrical redox reaction using electrodes, enabling material transformation to be performed using light energy.
  • the technology for performing material transformation using light energy involves no discharge of carbon dioxide and allows the use of sunlight or the like that is natural energy. The technology is thus expected to be applied in the fields of energy, environments, and the like. Studies have been conducted about merger of a photoelectric conversion mechanism and a catalytic technology for purifying contaminants and producing valuables, realizing a sound material-cycle society system.
  • a photocatalytic apparatus includes a first electrode disposed in an electrolytic solution or in steam and functioning as an anode, and a second electrode electrically connected to the first electrode and disposed in an electrolytic solution or in steam, the second electrode functioning as a cathode.
  • the first electrode includes a first transparent conductive substrate having light transmittivity and electrical conductivity, a first light power generation layer that is disposed on the first transparent conductive substrate and absorbs light to generate electrons and holes, and a photocatalytic layer that is disposed on the first light power generation layer and catalyzes an oxidation reaction when being irradiated with light.
  • the second electrode 20 is an electrode functioning as a cathode, and performs photovoltaic generation to separate electrons from holes on the basis of the photovoltaic action, and performs a reduction reaction catalyzed by an intended electrode catalyst.
  • the second electrode 20 uses the photovoltaic action and the catalytic action catalyzed by the electrode catalyst to reduce an oxidant contained in the electrolytic medium to perform material transformation of the oxidant into a predetermined product.
  • first electrolytic solution 110 and the second electrolytic solution 210 include seawater, lake water, river water, domestic wastewater, factory wastewater, treated water thereof, tap water, industrial water, special wastewater with a carbon content, a nitrogen content, a sulfur content, or the like, and the like.
  • the first electrolysis cell 100 connects to a first gas feeding apparatus 101, a first gas discharge apparatus 102, a first electrolytic solution feeding apparatus 103, and a first electrolytic solution discharge apparatus 104 each via piping.
  • the second electrolysis cell 200 connects to a second gas feeding apparatus 201, a second gas discharge apparatus 202, a second electrolytic solution feeding apparatus 203, and a second electrolytic solution discharge apparatus 204 each via piping.
  • the second electrolytic solution feeding apparatus 203 feeds the second electrolysis cell 200 with the second electrolytic solution 210 containing a predetermined oxidant. Additionally, the second electrolytic solution discharge apparatus 204 discharges, from the second electrolysis cell 200, the second electrolytic solution 210 containing a product generated by reduction of the oxidant, with the second electrolytic solution 210 recovered.
  • a voltmeter 60 is installed in the photocatalytic apparatus 1.
  • the voltmeter 60 is electrically connected in parallel to external wiring and a reference electrode 61.
  • the reference electrode 61 is installed inside the first electrolysis cell 100 and immersed in the first electrolytic solution 110.
  • the first conductive layer 12 permits external light to be transmitted to the first light power generation layer 14 and the photocatalytic layer 15 and functions as a current collector for the first electrode 10.
  • the first conductive layer 12 is electrically connected to the second electrode 20 via external wiring.
  • the first conductive layer 12 is formed of a material exhibiting light transmittivity for the irradiation light and having high electrical conductivity.
  • Examples of a material for the first electron transport layer 13 include oxide semiconductors such as titanium oxide (TiOz), zinc oxide (ZnO), tin oxide (SnOz), magnesium oxide (MgO), molybdenum trioxide (MoOs), and niobium oxide (NbO), which are metal excessive, and the oxide semiconductors doped with Cr, Mn, Fe, Co, Ni, Cu, Ru, Rh, Pd, In, Sn, Sb, and the like, metal complexes, and organic materials such as fluorene derivative, oxadiazole derivative, and benzodiazole derivative.
  • oxide semiconductors such as titanium oxide (TiOz), zinc oxide (ZnO), tin oxide (SnOz), magnesium oxide (MgO), molybdenum trioxide (MoOs), and niobium oxide (NbO), which are metal excessive
  • oxide semiconductors doped with Cr, Mn, Fe, Co, Ni, Cu, Ru, Rh, Pd, In, Sn
  • Provision of the first electron transport layer 13 enables a reduction in loss of charge at the interface between the first light power generation layer 14 and another layer. Additionally, electrons in the first light power generation layer 14 can be selectively transported toward the first conductive layer 12, while migration of holes is inhibited. When electrons generated in the first light power generation layer 14 are separated by band bending, the electrons are difficult to recouple to holes generated in the first light power generation layer 14. The first light power generation layer 14 increases light energy conversion efficiency, thus enabling an increase in the efficiency of material transformation by the first electrode 10.
  • the first light power generation layer 14 is a layer using light energy and absorbs light to generate electrons and holes. Electrons generated in the first light power generation layer 14 are transported to the first conductive layer 12 side. Holes generated in the first light power generation layer 14 are transported to the photocatalytic layer 15 side.
  • the first light power generation layer 14 is formed of a material exhibiting a photovoltaic action and absorbing light to generate electrons and holes. The material causes band bending toward the interface to separate the electrons from the holes.
  • a material for the first light power generation layer 14 includes a valence band having an energy level higher than that of a redox potential of a predetermined reductant contained in the first electrolytic solution 110.
  • Examples of the material for the first light power generation layer 14 include bismuth oxyiodide (BiOI), bismuth oxybromide (BiOBr), bismuth oxychloride (BiOCI), a composite material of any of the above-listed materials and an electron mediator, a semiconductor composite material of pn joined semiconductors or pin joined semiconductors, and the like.
  • the semiconductor examples include oxide semiconductors such as titanium oxide, zinc oxide, tin oxide, molybdenum trioxide, gallium oxide, nickel oxide (II), copper oxide (I), bismuth tungstate, bismuth vanadium oxide, tin niobate, strontium titanate, and iridium oxide zinc oxide doped with Cr, Mn, Fe, Co, Ni, Cu, Ru, Rh, Pd, In, Sn, or Sb, sulfides such as cadmium sulfide, copper indium sulfide, and copper zinc tin sulfide, selenides such as cadmium selenium, copper indium selenide, and copper gallium selenide, tellurides such as copper gallium telluride and cadmium tellurium, nitrides such as niobium nitride and tantalum nitride, amorphous silicon, crystal silicon, and the like, germanium, impurity semiconductors such as a two
  • the material of the first light power generation layer 14 preferably includes a band gap smaller than that of the material of the photocatalytic layer 15 in view of conjugation of the photovoltaic action of the first light power generation layer 14 with the photocatalytic action of the photocatalytic layer 15. Additionally, the material for the first light power generation layer 14 preferably includes a valence band having an energy level lower than that of a valence band of the material for the photocatalytic layer 15 in view of separation of electrons. In addition, the material for the first light power generation layer 14 preferably includes a conduction band having an energy level higher than that of a conduction band of the material for the photocatalytic layer 15 in view of separation of holes.
  • the first light power generation layer 14 With the first light power generation layer 14 provided, light radiated to the first electrode 10 causes a photovoltaic action to generate electrons and holes, and band bending allows the electrons generated to be separated from the holes generated, with the electrons migrated to the internal layer side and the holes migrated to the interface side.
  • the electrons and the holes separated from one another can be used for a redox reaction at the respective electrodes, allowing material transformation to be achieved with high energy efficiency.
  • the promotor 16 assists a catalytic action performed by the photocatalytic layer 15.
  • the promotor 16 used may be of a type providing a reaction field for the oxidation reaction by the photocatalytic layer 15, a type promoting generation of predetermined gas, a type adjusting optical responsivity for visible light, or the like.
  • the second electrode 20 includes a second transparent substrate 21, a second conductive layer 22, a charge transport layer 23, a second light power generation layer 24, a second electron transport layer 25, a conductive reflection layer 26, and a catalytic layer 27.
  • the second transparent substrate 21 and the second conductive layer 22 form a second transparent conductive substrate having light transmittivity and electrical conductivity.
  • the second conductive layer 22 permits external light to be transmitted to the second light power generation layer 24 and functions as a current collector for the second electrode 20.
  • the second conductive layer 22 is electrically connected to the first electrode 10 via external wiring.
  • the second conductive layer 22 is formed of a material exhibiting light transmittivity for the irradiation light and having high electrical conductivity.
  • Examples of a material for the second conductive layer 22 include indium tin oxide (ITO), a fluorine-doped tin oxide (FTO), indium oxide zinc oxide (IZO), gallium oxide zinc oxide (GZO), aluminum-doped zinc oxide (AZO), zinc oxide (ZnO), tin oxide (SnOz), and the like.
  • ITO indium tin oxide
  • FTO fluorine-doped tin oxide
  • IZO indium oxide zinc oxide
  • GZO gallium oxide zinc oxide
  • AZO aluminum-doped zinc oxide
  • ZnO zinc oxide
  • SnOz tin oxide
  • Examples of a material for the charge transport layer 23 include, as materials having high hole transportability, nickel oxide (II) (NiO), ferroxide (II) (FeO), copper oxide (I) (CuzO), copper oxide (II) (CuO), and the like, oxide semiconductors including the above-listed materials doped with heterogenous elements, compound semiconductors such as copper iodide (CuI) and copper thiocyanate (I) (CuSCN), metal complexes, and organic materials such as triaryl amine derivative, phthalocyanine derivative, and oxazole derivative.
  • Examples of a material for the second electron transport layer 25 include oxide semiconductors such as titanium oxide (TiOz), zinc oxide (ZnO), tin oxide (SnO 2 ), magnesium oxide (MgO), and niobium oxide (NbO), which are metal excessive, and these oxide semiconductors doped with Cr, Mn, Fe, Co, Ni, Cu, Ru, Rh, Pd, In, Sn, Sb, and the like, lithium fluorine (LiF), fluorocarbon, metal complexes, and organic materials such as fluorene derivative, oxadiazole derivative, and benzodiazole derivative.
  • oxide semiconductors such as titanium oxide (TiOz), zinc oxide (ZnO), tin oxide (SnO 2 ), magnesium oxide (MgO), and niobium oxide (NbO), which are metal excessive, and these oxide semiconductors doped with Cr, Mn, Fe, Co, Ni, Cu, Ru, Rh, Pd, In, Sn, Sb, and the like, lithium fluor
  • Provision of the second electron transport layer 25 enables a reduction in loss of charge at the interface between the second light power generation layer 24 and another layer. Additionally, electrons in the second light power generation layer 24 can be selectively transported toward the catalytic layer 27, while migration of holes is inhibited. Electrons generated in the second light power generation layer 24 and electrons transported from the first electrode 10 are difficult to recouple to holes generated in the second light power generation layer 24.
  • the second light power generation layer 24 increases light energy conversion efficiency, thus enabling an increase in the efficiency of material transformation by the second electrode 20.
  • the conductive reflection layer 26 has electrical conductivity and transports electrons from the second light power generation layer 24 side toward the catalytic layer 27 side.
  • the conductive reflection layer 26 controls the conduction of charge at the interface between the second light power generation layer 24 side and the catalytic layer 27 side, and reflects irradiation light toward the second light power generation layer 24 side.
  • the conductive reflection layer 26 is formed of a material having a high reflectance for visible light, ultraviolet light, and the like, a small work function, and high electron conductivity.
  • Provision of the conductive reflection layer 26 enables irradiation light to be reflected and radiated to the second light power generation layer 24 side. Additionally, provision of the conductive reflection layer 26 reduces a junction barrier at the interface between the second light power generation layer 24 side and the catalytic layer 27 side, allowing electron conduction and rectification at the interface to be improved. In a case where the catalytic layer 27 side is directly deposited on the front surface of the second electron transport layer 25, the interface is nonuniform, and conduction paths of electrons locally concentrate in the plane, leading to variation in potential difference. In contract, provision of the conductive reflection layer 26 reduces variation in conduction resistance, allowing electrons to be transported uniformly in an edgewise direction orthogonal to the lamination direction of the electrode elements.
  • Materials for each of the layers constituting the first electrode 10 and the second electrode 20 can be synthesized using an appropriate synthesis method such as metal organic decomposition (MOD), hydrothermal synthesis, solution phase synthesis, or sol-gel synthesis.
  • the promotor 16 can be supported using PVD such as vacuum deposition or sputtering, electrodeposition, chemical deposition, adsorption, or the like.
  • the first light power generation layer 14 When the irradiation light is incident on the first light power generation layer 14, electrons in the first light power generation layer 14 are excited by the conduction band and separated from holes. The electrons generated in the first light power generation layer 14 are transported to the first conductive layer 12 via the first electron transport layer 13. The electrons transported to the first conductive layer 12 are transported to the second conductive layer 22 via external wiring. The holes generated in the first light power generation layer 14 are transported to the photocatalytic layer 15.
  • the electrons in the photocatalytic layer 15 are excited by the conduction band to generate electrons and holes in the material.
  • the reductant contained in the first electrolytic solution 110 receives, due to the oxidation reaction by the photocatalytic layer 15, holes generated by the photocatalytic layer 15 and the first light power generation layer 14, and is transformed into a predetermined product. Some or all of the electrons generated in the photocatalytic layer 15 recouple to the holes generated in the first light power generation layer 14, with the remaining electrons transported to the first conductive layer 12.
  • the product resulting from the oxidation reaction is recovered by the first electrolytic solution discharge apparatus 104.
  • the electrons in the second light power generation layer 24 are excited by the conduction band and separated from the holes. Holes generated in the second light power generation layer 24 are transported toward the charge transport layer 23. Electrons generated in the second light power generation layer 24 are transported to the catalytic layer 27 via the second electron transport layer 25 and the like.
  • the electrical reduction reaction by the catalytic layer 27 is promoted. Some or all of the electrons generated in the first light power generation layer 14 recouple to the holes generated in the second light power generation layer 24, with the remaining electrons transported to the catalytic layer 27.
  • the oxidant contained in the second electrolytic solution 210 receives, due to the reduction reaction by the catalytic layer 27, the electrons generated by the second light power generation layer 24 and the first light power generation layer 14, and is transformed into a predetermined product.
  • the product resulting from the reduction reaction is recovered by the second electrolytic solution discharge apparatus 204.
  • the anode side uses the photocatalytic action to allow material transformation to be inexpensively performed on the basis of oxidation power using light energy.
  • both the anode-side electrode and the cathode-side electrode use the photovoltaic action, and thus the utilization rate of the light energy can be increased to improve the material transformation efficiency based on the electrode reaction.
  • Light power generation performed at both electrodes allows reduction of the auxiliary potential or abolishment of the external power supply with a potential difference ensured that is required for the redox reaction, enabling a reduction in the material transformation cost as a whole.
  • conjugation of the photocatalyst with the light power generation layer makes mutual migration and mutual use of charge efficient to allow the utilization rate of the light energy to be increased.
  • FIG. 2 is a diagram schematically depicting a photocatalytic apparatus according to a second embodiment of the present invention.
  • a photocatalytic apparatus 2 includes the first electrode 10 functioning as an anode, the second electrode 20 functioning as a cathode, the electrolysis cells 100 and 200, and the like as with the photocatalytic apparatus 1 described above.
  • the promotor layer 17 is a layer that assists the catalytic action by the photocatalytic layer 15.
  • the promotor layer 17 used may be of a type providing a reaction field for the oxidation reaction by the photocatalytic layer 15, a type promoting generation of predetermined gas, a type adjusting optical responsivity for visible light, or the like.
  • the promotor layer 17 may be either porous or non-porous.
  • the promotor layer 17 is preferably porous in view of reaction efficiency.
  • Examples of a material for the promotor layer 17 include metals such as copper, silver, gold, platinum, palladium, rhodium, and ruthenium, and metal oxides such as chromium oxide, copper oxide, ferroxide, nickel oxide, manganese oxide, cobalt oxide, platinum oxide, and chromium oxide, and the like.
  • Examples of the deposition method for forming the promotor layer 17 include PVD such as vacuum deposition or sputtering, CVD such as plasma CVD or organic metal CVD, CSD, and the like.
  • the promotor layer 17 can be patterned in any shape on the front surface of the photocatalytic layer 15.
  • the photocatalytic apparatus 2 produces effects similar to those of the photocatalytic apparatus 1 described above. Additionally, the formation of the promotor layer 17 on the front surface of the photocatalytic layer 15 allows possible drop-off or elution of the promotor to be prevented, compared to the support of promotor particles on the front surface. Additionally, the promotor can be uniformly disposed on the front surface of the photocatalytic layer 15, thus enabling a reduction in variation in migration of charge to the promotor in the edgewise direction orthogonal to the lamination direction of the electrode elements.
  • the photocatalytic apparatus 3 differs from the photocatalytic apparatus 1 described above in that an insulator is embedded in the first electrode 10, and that the electrode elements of the first electrode 10 are divided into cell structures by the insulator 18.
  • the other main configuration of the photocatalytic apparatus 3 is similar to that of the photocatalytic apparatus 1 described above.
  • the insulator 18 can be provided in an appropriate shape as viewed in the lamination direction of the electrode elements.
  • Examples of the shape of the cell units into which the electrode elements are partitioned by the insulator 18 include polygons such as a rectangle, a rhombus, and a hexagon.
  • the insulator 18 can be provided as slits, squares, or the like as viewed in the lamination direction of the electrode elements.
  • the insulator 18 is formed to penetrate the first electron transport layer 13, the first light power generation layer 14, and the photocatalytic layer 15 in the lamination direction of the electrode elements.
  • the insulator 18 can be formed to penetrate one or more of the first electron transport layer 13, the first light power generation layer 14, and the photocatalytic layer 15.
  • the insulator 18 is preferably formed to penetrate at least the first electron transport layer 13.
  • the photocatalytic apparatus 3 produces effects similar to those of the photocatalytic apparatus 1 described above. Additionally, the insulator 18 is embedded in the first electrode 10, and the electrode elements of the first electrode 10 are divided into cell structures, thus allowing the conduction paths of charge to be partitioned along the lamination direction of the electrode elements. The conduction paths of charge can be limited along the lamination direction of the electrode elements, thus enabling a reduction in scattering loss or recoupling loss of charge. Additionally, the conduction paths of charge are discretized in the edgewise direction orthogonal to the lamination direction of the electrode elements, thus allowing prevention of local concentration of the conduction paths of charge in the plane. The conduction paths are less likely to have extremely low potentials, and potential differences are made unlikely to vary, thus allowing improvement of the efficiency of material transformation by the first electrode 10.
  • a photocatalytic apparatus 4 includes the first electrode 10 functioning as an anode, the second electrode 20 functioning as a cathode, the electrolysis cells 100 and 200, and the like as with the photocatalytic apparatus 1 described above.
  • the photocatalytic apparatus 4 according to the present embodiment differs from the photocatalytic apparatus 1 described above in that a thin line structure 19 is formed on the front surface of the first electron transport layer 13 on the first light power generation layer 14 side.
  • the other main configuration of the photocatalytic apparatus 4 is similar to that of the photocatalytic apparatus 1 described above.
  • the thin line structure 19 forms transport paths through which electrons are selectively transported along the lamination direction of the electrode elements.
  • the thin line structure 19 is embedded in the first light power generation layer 14 in a state of protruding from the front surface of the first electron transport layer 13 toward the first light power generation layer 14 side and extending along the lamination direction of the electrode elements of the first electrode 10.
  • the thin line structure 19 is formed of a crystal shaped like rods, needles, or the like.
  • the thin line structure 19 is formed of a material similar to that of the first electron transport layer 13.
  • FIG. 5 is a diagram schematically depicting a photocatalytic apparatus according to a fifth embodiment of the present invention.
  • the photocatalytic apparatus 5 differs from the photocatalytic apparatus 1 described above in that a conductive adhesion layer 28 is formed between the conductive reflection layer 26 and the catalytic layer 27, with an insulator 29 embedded in the second electrode 20.
  • the other main configuration of the photocatalytic apparatus 5 is similar to that of the photocatalytic apparatus 1 described above.
  • Examples of a material for the conductive adhesion layer 28 include a composite material of a conducting agent and matrix resin, a conductive oxide, and the like.
  • Examples of the conducting agent include carbon nanotube, carbon fiber, carbon black, and graphene.
  • Examples of the matrix resin include epoxy resin, phenol resin, and the like.
  • Examples of the conductive oxide include zinc oxide (ZnO), tin oxide (SnO 2 ), and the like.
  • the insulator 29 can be provided in an appropriate shape as viewed in the lamination direction of the electrode elements.
  • Examples of the partitioning shape of the cell units of the insulator 29 include polygons such as a rectangle, a rhombus, and a hexagon.
  • the insulator 29 can be provided as slits, squares, or the like as viewed in the lamination direction of the electrode elements.
  • Examples of the deposition method for depositing the conductive adhesion layer 28 and the insulator 29 include PVD such as vacuum deposition or sputtering, CVD such as plasma CVD or organic metal CVD, CSD, and the like.
  • the insulator 29 can be formed by a method of performing patterning using a mask, a method of combining etching and deposition, or the like.
  • FIG. 6 is a diagram depicting an example of a relation between an electrode potential and a current density of a known photocatalytic electrode.
  • FIG. 7 is a diagram depicting an example of a relation between an output time and the current density of the known photocatalytic electrode.
  • FIG. 6 and FIG. 7 depict results of analysis of electrode characteristics of a photocatalytic electrode using a photocatalyst, by a photoelectric converting apparatus including the photocatalytic electrode and a reference electrode.
  • FIG. 6 depicts results of linear scanning voltammetry in which a linear electrode potential has been swept.
  • FIG. 7 depicts results of measurement of variation in current density when 1 V of electrode potential is generated.
  • the photocatalytic electrode used is an electrode including a photocatalytic layer laminated on a transparent conductive substrate.
  • the photocatalytic layer was formed of bismuth vanadium oxide (BiVo 4 ) and had a film thickness of 200 nm.
  • the reference electrode used is platinum wiring. The photocatalytic electrode and the reference electrode were immersed in a 0.1-mol/L sodium sulfate solution.
  • the photocatalytic electrode was irradiated with simulated sunlight.
  • a light source used is a solar simulator HAL-C100 (Asahi Spectra Co., Ltd.). Simulated sunlight adjusted to a standard value of AM1.5G was adjusted to an intensity output (0.6 SUN) corresponding to 60% of the solar light intensity, and the adjusted simulated sunlight was radiated to the surface of the photocatalytic layer of the photocatalytic electrode.
  • the horizontal axis indicates the electrode potential [V vs. Ag/AgCI] of the photocatalytic electrode, and the vertical axis indicates the current density (mA/cm 2 ) of the photocatalytic electrode.
  • a solid curve in FIG. 6 indicates results of no light irradiation, and a dashed curve indicates results of light irradiation.
  • the horizontal axis indicates the output time (seconds) of the photocatalytic electrode, and the vertical axis indicates the current density (mA/cm 2 ) of the photocatalytic electrode. The current density of the photocatalytic electrode was determined by dividing the conducting current to the photocatalytic electrode by the electrode area immersed in the electrolytic solution and irradiated with light.
  • the first electrolysis cell 100 and the second electrolysis cell 200 accommodate the electrolytic solutions 110 and 210, which are liquid.
  • electrolytic medium conductive steam that can transport charge may be sealed in the first electrolysis cell 100 and the second electrolysis cell 200.
  • feeding of a reductant and an oxidant and recovery of a product can be performed by the first gas feeding apparatus 101, the first gas discharge apparatus 102, the second gas feeding apparatus 201, and the second gas discharge apparatus 202.

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EP23203871.1A 2022-12-28 2023-10-16 Photokatalytische vorrichtung Pending EP4394084A3 (de)

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JP2022212561A JP2024095341A (ja) 2022-12-28 2022-12-28 光触媒装置

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EP4394084A2 true EP4394084A2 (de) 2024-07-03
EP4394084A3 EP4394084A3 (de) 2024-08-14

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