US20160362801A1 - Photoelectrochemical reaction system - Google Patents

Photoelectrochemical reaction system Download PDF

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US20160362801A1
US20160362801A1 US15/247,178 US201615247178A US2016362801A1 US 20160362801 A1 US20160362801 A1 US 20160362801A1 US 201615247178 A US201615247178 A US 201615247178A US 2016362801 A1 US2016362801 A1 US 2016362801A1
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Prior art keywords
reduction
reaction
reaction solution
electrode
oxidation
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Chingchun Huang
Satoshi Mikoshiba
Akihiko Ono
Ryota Kitagawa
Yuki Kudo
Jun Tamura
Eishi TSUTSUMI
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Toshiba Corp
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Toshiba Corp
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/04—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices
    • H01L31/06—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices characterised by potential barriers
    • H01L31/072—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices characterised by potential barriers the potential barriers being only of the PN heterojunction type
    • H01L31/0725—Multiple junction or tandem solar cells
    • 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
    • C25B3/04—
    • C25B1/003—
    • 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
    • C25B1/06—
    • 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
    • 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
    • C25B9/06—
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/04—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices
    • H01L31/054—Optical elements directly associated or integrated with the PV cell, e.g. light-reflecting means or light-concentrating means
    • H01L31/056—Optical elements directly associated or integrated with the PV cell, e.g. light-reflecting means or light-concentrating means the light-reflecting means being of the back surface reflector [BSR] type
    • 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
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy
    • Y02E10/52—PV systems with concentrators
    • 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

  • Embodiments disclosed herein generally relate to a photoelectrochemical reaction system.
  • the plants use a system which is excited in two stages by the light energy called as a Z scheme. Namely, the plants obtain electrons from water (H 2 O) by the light energy, and synthesize cellulose and saccharide by reducing carbon dioxide (CO 2 ) using the electrons.
  • a photoelectrochemical reaction device reducing (decomposing) CO 2 by the light energy has been advanced.
  • a device in a two-electrode system in which an electrode having a reduction catalyst reducing carbon dioxide (CO 2 ) and an electrode having an oxidation catalyst oxidizing water (H 2 O) are included, and these electrodes are immersed in water where CO 2 is dissolved.
  • CO 2 reduction catalyst reducing carbon dioxide
  • H 2 O oxidation catalyst oxidizing water
  • a dissolved concentration of CO 2 is low, and therefore, it is impossible to increase a decomposition efficiency of CO 2 .
  • an aqueous solution containing amine molecules, an ionic liquid, and so on have been studied.
  • an alkaline solution such as an aqueous potassium hydroxide solution and an aqueous sodium hydroxide solution, or an amine solution is used as the electrolytic solution in a conventional CO 2 reductor (CO 2 electrolytic device).
  • the amine solution used as the CO 2 absorbent has low chemical stability, and it is gradually oxidized under a natural state.
  • An oxidation electrode side of the photoelectrochemical reactor is in a strong oxidation environment, and therefore, amine molecules in the aqueous solution are preferentially oxidized, and a recovery and a reuse of the amine solution cannot be performed.
  • an inside of an electrolytic vessel is isolated into an oxidation electrode side and a reduction electrode side.
  • this incurs complication of a cell structure, and therefore, a device cost increases, and the device is easy to be further large-sized.
  • the ionic liquid is chemically stable, but it is expensive in itself, and therefore, the device cost increases.
  • a transport property and a transport efficiency of CO 2 from a device discharging CO 2 to the electrolytic device are not considered, and a configuration as a photoelectrochemical reaction system is not developed.
  • FIG. 1 is a configuration chart of a photoelectrochemical reaction system according to a first embodiment.
  • FIG. 2 is a view illustrating a first example of a photoelectrochemical module used for the photoelectrochemical reaction system illustrated in FIG. 1 .
  • FIG. 3 is a view illustrating a second example of a photoelectrochemical module used for the photoelectrochemical reaction system illustrated in FIG. 1 .
  • FIG. 4 is a view illustrating an oxidation electrode used for the photoelectrochemical module illustrated in FIG. 2 .
  • FIG. 5 is a view illustrating a reduction electrode used for the photoelectrochemical module illustrated in FIG. 2 .
  • FIG. 6 is a view illustrating a photoelectric conversion element used for the photoelectrochemical module illustrated in FIG. 2 .
  • FIG. 7 is a view illustrating a concrete example of the photoelectric conversion element illustrated in FIG. 6 .
  • FIG. 8 is a view explaining operations of the photoelectrochemical module illustrated in FIG. 2 .
  • FIG. 9 is a view explaining operations of the photoelectrochemical module illustrated in FIG. 3 .
  • FIG. 10 is a configuration chart of a photoelectrochemical reaction system according to a second embodiment.
  • a photoelectrochemical reaction system including: a conversion part converting carbon dioxide into at least one intermediate substance selected from the group consisting of a metal carbonate and a metal hydrogen carbonate by an aqueous solution containing a metal hydroxide, and generating a reaction solution containing the intermediate substance; a transfer part transferring the reaction solution containing the intermediate substance; and a reduction part including a one-liquid reaction vessel where the reaction solution is led in by the transfer part, an oxidation electrode immersed in the reaction solution to oxidize water; a reduction electrode immersed in the reaction solution to reduce the intermediate substance, and a photoelectric conversion element electrically connected to the oxidation and reduction electrodes and performing a charge separation by light energy.
  • FIG. 1 is a view illustrating a configuration of a photoelectrochemical reaction system according to a first embodiment.
  • a photoelectrochemical reaction system 100 of the first embodiment is provided subsidiary to a CO 2 generation part 100 X which generates gas containing carbon dioxide (CO 2 ).
  • the photoelectrochemical reaction system 100 includes a CO 2 conversion part 102 , a reaction solution transfer part 103 , a CO 2 reduction part 104 , a reaction solution adjustment part 105 , a reaction solution reflux part 106 , a product collection part 107 , and a reaction solution storage part 108 .
  • a power station can be cited.
  • the CO 2 generation part 100 X is not limited thereto, and may be an ironwork, a chemical factory, a garbage incineration plant, or the like.
  • the CO 2 generation part 100 X is not particularly limited.
  • the photoelectrochemical reaction system 100 according to the embodiment is able to enable reduction in size of the CO 2 reduction part 104 as described later, and therefore, it is effective for small-sized plants such as the garbage incineration plant without being limited to large-sized plants such as the power station and the ironwork.
  • the gas containing CO 2 generated at the CO 2 generation part 100 X for example, exhaust gas discharged from the power station, the ironwork, the chemical factory, the garbage incineration plant, or the like is transferred to the CO 2 conversion part 102 of the photoelectrochemical reaction system 100 .
  • the exhaust gas may be transferred to the CO 2 conversion part 102 after impurities such as sulfur oxide in the exhaust gas are removed depending on components and so on of the exhaust gas discharged from the CO 2 generation part 100 X.
  • the photoelectrochemical reaction system 100 may include an impurity removal part 101 .
  • the impurity removal part 101 is not limited to be arranged between the CO 2 generation part 100 X and the CO 2 conversion part 102 , and may be arranged everywhere in a circulation route of carbon dioxide.
  • the impurity removal part 101 may be arranged between the CO 2 conversion part 102 , the reaction solution transfer part 103 , the CO 2 reduction part 104 , the reaction solution reflux part 106 , and the reaction solution storage part 108 .
  • the impurities is not limited to the component in the exhaust gas, and may be a decomposing material and a chemically changed material of a pipe and the reaction solution, a eluted material from a pipe and a tank by the reaction solution, metal ions from the CO 2 reduction part 104 and so on.
  • the impurity removal part 101 various dry-type or wet-type gas processing apparatuses, a ion-exchange resin absorbing metal ions, a filter removing sulfur oxides and nitrogen oxides, a filter removing a physical decomposing material of a pipe, a tank and a stirrer, and so on can be cited.
  • CO 2 is converted into at least one intermediate substance selected from a metal carbonate and a metal hydrogen carbonate.
  • the CO 2 conversion part 102 includes a reaction tank where an aqueous solution containing a metal hydroxide which converts CO 2 into the intermediate substance is accommodated.
  • gas containing CO 2 is injected from a gas supply pipe.
  • CO 2 injected into the aqueous solution is converted into at least one intermediate substance selected from the metal carbonate and the metal hydrogen carbonate by the metal hydroxide.
  • CO 2 is converted into the intermediate substance by the metal hydroxide, and thereby, a reaction solution (aqueous solution) containing the intermediate substance is generated in the reaction tank.
  • the reaction solution (aqueous solution) containing at least one intermediate substance selected from the metal carbonate and the metal hydrogen carbonate and water (H 2 O) is generated.
  • the metal hydroxide which converts CO 2 into the intermediate substance is preferably a hydroxide of at least one metal selected from an alkaline metal (group 1 element) and an alkaline earth metal (group 2 element).
  • the metal hydroxide is more preferably the hydroxide of at least one metal selected from lithium (Li), sodium (Na), potassium (K), rubidium (Rb), beryllium (Be), magnesium (Mg), calcium (Ca), and strontium (Sr).
  • a pH of the aqueous solution containing the metal hydroxide is preferably adjusted to a range of 7 to 14.
  • the pH of the aqueous solution containing the metal hydroxide is preferably adjusted to a weak alkaline region.
  • the reaction solution (aqueous solution) containing the intermediate substance (the metal carbonate and the metal hydrogen carbonate) generated at the CO 2 conversion part 102 is transferred to the CO 2 reduction part 104 by the reaction solution transfer part 103 .
  • the CO 2 conversion part 102 and the CO 2 reduction part 104 are not necessarily operated simultaneously. For example, when the operation of the CO 2 reduction part 104 is stopped at night though the CO 2 conversion part 102 operates also at night, the reaction solution containing the intermediate substance generated at the CO 2 conversion part 102 is stored at the reaction solution storage part 108 . The reaction solution stored at the reaction solution storage part 108 is transferred to the CO 2 reduction part 104 at the operation time of the CO 2 reduction part 104 .
  • the CO 2 reduction part 104 includes a photoelectrochemical module 1 illustrated in FIG. 2 and FIG. 3 .
  • FIG. 2 illustrates a photoelectrochemical module 1 A in which a photoelectric conversion element is disposed outside the reaction solution, and an oxidation electrode and a reduction electrode are immersed in the reaction solution.
  • FIG. 3 illustrates a photoelectrochemical module 1 B in which a stack (photoelectrochemical cell) of the oxidation electrode, a photoelectric conversion layer, and the reduction electrode is immersed in the reaction solution.
  • the photoelectrochemical module 1 A ( 104 ) illustrated in FIG. 2 includes a one-liquid type reaction vessel 3 accommodating a reaction solution 2 , an oxidation electrode 4 and a reduction electrode 5 immersed in the reaction solution 2 , and a photoelectric conversion element 6 disposed at outside the reaction vessel 3 and electrically connected to the oxidation electrode 4 and the reduction electrode 5 .
  • the reaction solution containing the intermediate substance generated at the CO 2 conversion part 102 is led in via the reaction solution lead-in pipe 7 a.
  • a lead-in amount of the reaction solution is adjusted to generate a predetermined space S at an upper part of the reaction vessel 3 .
  • the gaseous product generated by an oxidation-reduction reaction in the reaction vessel 3 is collected at the upper space S of the reaction vessel 3 , and thereafter, transferred to the product collection part 107 via the product send-out pipe 7 e.
  • the adjustment liquid is further led in according to need via the adjustment liquid lead-in pipe 7 b.
  • the reaction solution in the reaction vessel 3 is adjusted by the adjustment liquid to have a desired concentration, characteristics, and so on.
  • reaction solution in which the oxidation-reduction reaction is performed in the reaction vessel 3 is refluxed to the CO 2 conversion part 102 via the reaction solution lead-out pipe 7 c.
  • a part of the reaction solution after the reaction is discharged out of a system via the reaction solution discharge pipe 7 d according to need.
  • the lead-in and lead-out of the reaction solution may be continuously performed, or may be performed discontinuously in a batch mode.
  • the reaction vessel 3 is preferably formed by a material which does not chemically react with the reaction solution 2 , and difficult to be altered by the energy of sunlight.
  • a material for example, there can be cited resin materials such as a polyetheretherketone (PEEK) resin, a polyamide (PA) resin, a polyvinylidene fluoride (PVDF) resin, a polyacetal (POM) resin (copolymer), a polyphenyleneether (PPE) resin, an acrylonitrile butadiene styrene copolymer (ABS), a polypropylene (PP) resin, a polyethylene (PE) resin, and so on.
  • PEEK polyetheretherketone
  • PA polyamide
  • PVDF polyvinylidene fluoride
  • POM polyacetal
  • PPE polyphenyleneether
  • ABS acrylonitrile butadiene styrene copolymer
  • PP polypropylene
  • PE polyethylene
  • the reaction vessel 3 may include an agitator stirring the reaction solution 2 so that the reaction is uniformly and efficiently performed in the reaction vessel 3 .
  • the upper space S of the reaction vessel 3 is preferably a complete hermetical seal except the product send-out pipe 7 e to efficiently collect and discharge a gas product.
  • the reaction solution 2 is preferably led in to be within a range of 50% to 90% relative to an internal capacity of the reaction vessel 3 , and more preferably led in to be within a range of 70% to 90% of the reaction vessel 3 so as to keep the upper space S of the reaction vessel 3 .
  • the reaction solution 2 led into the reaction vessel 3 is adjusted to have the concentration and characteristics suitable for an oxidation reaction of H 2 O and a reduction reaction of the intermediate substance by the reaction solution adjustment part 105 .
  • a redox couple may be added to the reaction solution 2 according to need.
  • the redox couple for example, there can be cited Fe 3+ /Fe 2+ and IO 3 ⁇ /I ⁇ .
  • the oxidation electrode 4 includes, for example, a support substrate 4 a and oxidation catalyst layers 8 formed at both surfaces thereof as illustrated in FIG. 4 .
  • the support substrate 4 a of the oxidation electrode 4 is formed by a material having conductivity.
  • materials of the support substrate 4 a there can be cited metals such as Cu, Al, Ti, Ni, Fe, Ag, an alloy containing at least one of these metals, a conductive resin, and so on.
  • a metal plate and an alloy plate are used for the support substrate 4 a in consideration of formability of the oxidation catalyst layer 8 .
  • the support substrate 4 a may be constituted by a porous body of the metal, the alloy, and the conductive resin.
  • the oxidation catalyst layer 8 has functions receiving positive holes from the support substrate 4 a of the oxidation electrode 4 , reacting with H 2 O in the reaction solution 2 , and oxidizing H 2 O.
  • a composing material of the oxidation catalyst layer 8 preferably contains an oxide or a hydroxide of at least one metal selected from Fe, Ni, Co, Cu, Ti, V, Mn, Ru, and Ir.
  • the oxidation catalyst layer 8 As concrete composing materials of the oxidation catalyst layer 8 , there can be cited one or two or more composite materials selected from RuO 2 , NiO, Ni(OH) 2 , NiOOH, Co 3 O 4 , Co(OH) 2 , CoOOH, FeO, Fe 2 O 3 , MnO 2 , Mn 3 O 4 , Rh 2 O 3 , and IrO 2 .
  • the oxidation catalyst layer 8 is to accelerate the oxidation reaction of H 2 O at the oxidation electrode 4 , and therefore, it is possible not to have the oxidation catalyst layer 8 when a reaction rate of the oxidation reaction by the support substrate 4 a of the oxidation electrode 4 is enough.
  • the reduction electrode 5 includes a support substrate 5 a and reduction catalyst layers 9 formed at both surfaces thereof as illustrated in FIG. 5 .
  • the support substrate 5 a of the reduction electrode 5 is formed by a material having conductivity.
  • materials of the support substrate 5 a there can be cited metals such as Cu, Al, Ti, Ni, Fe, Ag, an alloy containing at least one of these metals, a conductive resin, and so on.
  • a metal plate and an alloy plate are used for the support substrate 5 a in consideration of formability of the reduction catalyst layer 9 .
  • the support substrate 5 a may be constituted by a porous body of the metal, the alloy, the conductive resin, or the like.
  • the reduction catalyst layer 9 has functions receiving electrons from the support substrate 5 a of the reduction electrode 5 , and reducing the intermediate substance in the reaction solution 2 , namely, the metal carbonate and the metal hydrogen carbonate, and CO 2 generated by these.
  • a composing material of the reduction catalyst layer 9 preferably contains metals such as Au, Ag, Zn, Cu, Hg, Cd, Pb, Ti, In, Sn, metal complexes such as a ruthenium complex, a rhenium complex, carbon materials such as graphene, CNT (carbon nanotube), fullerene, ketjen black, and so on.
  • the reduction catalyst layer 9 is to accelerate the reduction reaction of CO 2 at the reduction electrode 5 , and therefore, it is possible not to have the reduction catalyst layer 9 when a reaction rate of the reduction reaction by the support substrate 5 a of the reduction electrode 5 is enough.
  • the photoelectric conversion element 6 is electrically connected to the oxidation electrode 4 and the reduction electrode 5 , and thereby, electrons and positive holes are exchanged between the oxidation electrode 4 and the reduction electrode 5 .
  • the photoelectric conversion element 6 performs a charge separation by the light energy.
  • the photoelectric conversion element 6 there can be cited a pin junction, a pn junction, an amorphous silicon solar cell, a multijunction solar cell, a single crystal silicon solar cell, a polycrystalline silicon solar cell, a dye sensitized solar cell, an organic thin-film solar cell, and so on.
  • the photoelectric conversion element 6 It is necessary for the photoelectric conversion element 6 to create a potential difference which is higher than a difference between a standard oxidation-reduction potential of the oxidation reaction of H 2 O generated in the vicinity of the oxidation electrode 4 and a standard oxidation-reduction potential of the reduction reaction of CO 2 generated in the vicinity of the reduction electrode 5 .
  • the photoelectric conversion element 6 is one capable of providing the energy necessary for simultaneously generating the oxidation reaction of H 2 O and the reduction reaction of CO 2 .
  • the photoelectric conversion element 6 is made up of a first electrode layer 11 , a photoelectric conversion layer (photovoltaic layer) 31 , and a second electrode layer 21 as illustrated in FIG. 6 .
  • FIG. 7 illustrates a concrete example of the photoelectric conversion element 6 using the silicon solar cell (pin junction) as the photoelectric conversion layer 31 .
  • the second electrode layer 21 is formed by metals such as Cu, Al, Ti, Ni, Fe, Ag, an alloy such as SUS which contains at least one of these metals, a conductive resin, semiconductors such as Si and Ge, and so on.
  • a metal plate, an alloy plate, a resin plate, or a semiconductor substrate is used for the second electrode layer 21 .
  • the photoelectric conversion layer 31 is formed on the second electrode layer 21 .
  • the photoelectric conversion layer 31 is made up of a reflection layer 32 , a first photoelectric conversion layer 33 , a second photoelectric conversion layer 34 , and a third photoelectric conversion layer 35 .
  • the reflection layer 32 is formed on the second electrode layer 21 , and includes a first reflection layer 32 a and a second reflection layer 32 b formed in sequence from a lower part side. Metals such as Ag, Au, Al, Cu, an alloy containing at least one of these metals, and so on are used for the first reflection layer 32 a having light reflectivity and conductivity.
  • the second reflection layer 32 b is provided to enhance the light reflectivity by adjusting an optical distance.
  • the second reflection layer 32 b is joined to an n-type semiconductor layer of the later-described photoelectric conversion layer 31 , and therefore, it is preferably formed by a material having a light transmission property and in which an ohmic contact with the n-type semiconductor layer is possible.
  • Transparent conductive oxides such as ITO (indium tin oxide), zinc oxide (ZnO), FTO (fluorine-doped tin oxide), AZO (aluminum-doped zinc oxide), ATO (antimony-doped tin oxide) are used for the second reflection layer 32 b.
  • the first photoelectric conversion layer 33 , the second photoelectric conversion layer 34 , and the third photoelectric conversion layer 35 are solar cells each using a pin junction semiconductor, and light absorption wavelengths thereof are different. These are stacked in a planar state, and thereby, it is possible to absorb the light in a wide wavelength of the sunlight by the photoelectric conversion layer 31 , and to efficiently use the light energy of the sunlight.
  • the photoelectric conversion layers 33 , 34 , 35 are connected in series, and therefore, it is possible to obtain a high open-circuit voltage.
  • the first photoelectric conversion layer 33 is formed on the reflection layer 32 , and includes an n-type amorphous silicon (a-Si) layer 33 a, an intrinsic amorphous silicon germanium (a-SiGe) layer 33 b, and a p-type microcrystal silicon (mc-Si) layer 33 c formed in sequence from a lower part side.
  • the a-SiGe layer 33 b is a layer absorbing light in a long wavelength region at approximately 700 nm. At the first photoelectric conversion layer 33 , the charge separation occurs by the light energy in the long wavelength region.
  • the second photoelectric conversion layer 34 is formed on the first photoelectric conversion layer 33 , and includes an n-type a-Si layer 34 a, an intrinsic a-SiGe layer 34 b, and a p-type mc-Si layer 34 c formed in sequence from a lower part side.
  • the a-SiGe layer 34 b is a layer absorbing light in an intermediate wavelength region at approximately 600 nm.
  • the charge separation occurs by the light energy in the intermediate wavelength region.
  • the third photoelectric conversion layer 35 is formed on the second photoelectric conversion layer 34 , and includes an n-type a-Si layer 35 a, an intrinsic a-Si layer 35 b, and a p-type mc-Si layer 35 c formed in sequence from a lower part side.
  • the a-Si layer 35 b is a layer absorbing light in a short wavelength region at approximately 400 nm.
  • the charge separation occurs by the light energy in the short wavelength region.
  • the first electrode layer 11 is formed on the p-type semiconductor layer (the p-type mc-Si layer 35 c ) of the photoelectric conversion layer 31 .
  • the first electrode layer 11 is preferably formed by a material in which the ohmic contact with the p-type semiconductor layer is possible.
  • Metals such as Ag, Au, Al, Cu, an alloy containing at least one of these metals, transparent conductive oxides such as ITO, ZnO, FTO, AZO, ATO, and so on are used for the first electrode layer 11 .
  • the first electrode layer 11 may have, for example, a structure in which the metal and the transparent conductive oxide are stacked, a structure in which the metal and the other conductive materials are compound, a structure in which the transparent conductive oxide and the other conductive materials are compound, and so on.
  • irradiated light passes through the first electrode layer 11 to reach the photoelectric conversion layer 31 .
  • the first electrode layer 11 has light transmission property for the irradiated light.
  • the charge separation occurs by the light energy in each wavelength region of the irradiated light (sunlight and so on).
  • the positive holes are separated toward the first electrode layer 11 side, and the electrons are separated toward the second electrode layer 21 side, and thereby, an electromotive force is generated at the photoelectric conversion layer 31 . Accordingly, the first electrode layer 11 toward which the positive holes move is electrically connected to the oxidation electrode 4 , and the second electrode layer 21 toward which the electrons move is electrically connected to the reduction electrode 5 .
  • the photoelectric conversion layer 31 having a stacked structure of three photoelectric conversion layers is described as an example, but the photoelectric conversion layer 31 is not limited thereto.
  • the photoelectric conversion layer 31 may have a stacked structure of two or four or more photoelectric conversion layers.
  • One photoelectric conversion layer 31 may be used instead of the photoelectric conversion layer 31 in the stacked structure.
  • the photoelectric conversion layer 31 is not limited to the solar cell using the pin junction type semiconductor, but may be a solar cell using a pn junction type semiconductor.
  • the semiconductor layer is not limited to Si, Ge, and for example, may be compound semiconductors such as GaAs, GaInP, AlGaInP, CdTe, CuInGaSe. Note that FIG.
  • a light irradiation side is not limited to the p-type semiconductor layer, but may be an n-type semiconductor layer.
  • the positive holes moved toward the oxidation electrode 4 are bonded with electrons generated by the oxidation reaction.
  • the reduction reactions of the intermediate substance and CO 2 take place in the vicinity of the reduction electrode 5 toward which the electrons move.
  • the electrons moved toward the reduction electrode 5 are used for the reduction reaction.
  • CO 2 is generated from, for example, the metal carbonate and the metal hydrogen carbonate as the intermediate substance.
  • CO 2 generated by reactions of the metal carbonate and the metal hydrogen carbonate is reduced (obtains electrons) in the vicinity of the reduction electrode 5 .
  • CO 2 generated by the reactions of the metal carbonate and the metal hydrogen carbonate reacts with H + which is generated at the oxidation electrode 4 side, defuses in the reaction solution 2 , and moves toward the reduction electrode 5 side, and electrons which are generated by the charge separation in the photoelectric conversion element 6 and move toward the reduction electrode 5 , and CO and H 2 O are generated, for example.
  • the reactions from the (7) expression to the (9) expression are ones illustrating examples of the reactions in the vicinity of the reduction electrode 5 , and there is a case when CO and H 2 O are generated by direct reduction of the metal carbonate and the metal hydrogen carbonate.
  • the reduction reaction of the intermediate substance and CO 2 it indicates any one of the above-stated reactions.
  • the photoelectrochemical module 1 B ( 104 ) illustrated in FIG. 3 includes the one-liquid type reaction vessel 3 accommodating the reaction solution 2 , a photoelectrochemical cell immersed in the reaction solution 2 , namely, a stack 10 of an oxidation catalyst layer 12 , the oxidation electrode (first electrode) 11 , the photoelectric conversion layer 31 , the reduction electrode (second electrode) 21 , and a reduction catalyst layer 22 .
  • the photoelectrochemical module 1 B it is possible to enable simplification and so on of components compared to the photoelectrochemical module 1 A illustrated in FIG. 2 .
  • the reaction vessel 3 in the photoelectrochemical module 1 B ( 104 ) has a similar configuration (each pipe and so on) to the reaction vessel 3 of the photoelectrochemical module 1 A illustrated in FIG. 2 .
  • the photoelectrochemical cell 10 including the photoelectric conversion layer 31 is disposed in the reaction vessel 3 , and therefore, the reaction vessel 3 does not chemically react with the reaction solution 2 , and is made up of a material which transmits light, namely a material whose absorptance of light in a wavelength region of 250 nm to 1100 nm is low.
  • formation materials of the reaction vessel 3 as stated above, there can be cited quartz, a super white glass, polystyrene, methacrylate, and so on.
  • the reaction vessel 3 may be one in which only a window part for light irradiation is formed by the above-stated materials, and the other parts are made up of the above-stated resin materials.
  • the oxidation catalyst layer 12 is formed on the first electrode (oxidation electrode) 11 of the photoelectric conversion element 6 illustrated in FIG. 7
  • the reduction catalyst layer 22 is formed on the second electrode (reduction electrode) 21 .
  • a catalyst layer which is disposed at the light irradiation side between the oxidation catalyst layer 12 and the reduction catalyst layer 22 has the light transmission property.
  • the configuration of the photoelectrochemical cell 10 is not limited thereto, and it is possible to apply the pin junction, the pn junction, the amorphous silicon solar cell, the multijunction solar cell, the single crystal silicon solar cell, the polycrystalline silicon solar cell, the dye sensitized solar cell, the organic thin-film solar cell, and so on having the oxidation catalyst layer and the reduction catalyst layer. It is necessary for the photoelectrochemical cell 10 to create a potential difference which is higher than a difference between a standard oxidation-reduction potential of the oxidation reaction of H 2 O generated in the vicinity of the oxidation electrode 11 and a standard oxidation-reduction potential of the reduction reaction of CO 2 generated in the vicinity of the reduction electrode 21 . Namely, the photoelectrochemical cell 10 is one capable of providing the energy necessary for simultaneously generating the oxidation reaction of H 2 O and the reduction reaction of CO 2
  • the photoelectrochemical module 1 B illustrated in FIG. 3 it is preferable to constitute such that 50% or more of the light energy being an energy source required for the reaction reaches the photoelectric conversion layer 31 from outside of the reaction vessel 3 by passing through the reaction vessel 3 , the reaction solution 2 , and the oxidation catalyst layer 12 .
  • the metals such as Ag, Au, Al, Cu, the alloy containing at least one of these metals, and the transparent conductive oxides such as ITO, ZnO, FTO, AZO, ATO, and so on as stated above.
  • the oxidation electrode 11 of the photoelectrochemical cell 10 is described to be at the light irradiation side, but it is not limited thereto, and the reduction electrode 21 may be at the light irradiation side.
  • the composing materials of the oxidation catalyst layer 12 and the reduction catalyst layer 22 are as stated above.
  • the catalyst layer which is disposed at the light irradiation side between the oxidation catalyst layer 12 and the reduction catalyst layer 22 , further the electrode disposed at the light irradiation side between the oxidation electrode 11 and the reduction electrode 21 have the light transmission property.
  • the photoelectrochemical cell 10 may be a stack in which the oxidation catalyst layer 12 , the oxidation electrode 11 , the photoelectric conversion layer 31 , the reduction electrode 21 , and the reduction catalyst layer 22 are simply integrated, or one in which through holes are formed at the stack as stated above in a stacking direction as ion through holes. It is preferable to provide the through holes at the photoelectrochemical cell 10 to efficiently move H + ions and so on between the oxidation reaction and the reduction reaction, and a reaction efficiency thereby improves.
  • the through holes are provided to penetrate from the oxidation catalyst layer 12 being one surface layer to the reduction catalyst layer 22 being the other surface layer of the photoelectrochemical cell 10 .
  • the photoelectrochemical cell 10 is immersed in the one-liquid type reaction vessel 3 , and therefore, it is excellent in moving efficiency of H + ions and so on by the constitution in itself. It is also the same as the photoelectrochemical module 1 A illustrated in FIG. 2 .
  • the stirrer and so on may be provided at the reaction vessel 3 to accelerate diffusion of H + ions and so on.
  • the oxidation-reduction reaction similar to the photoelectrochemical module lA illustrated in FIG. 2 occurs as illustrated in FIG. 9 .
  • the sunlight and so on irradiated on the reaction vessel 3 reaches the photoelectrochemical cell 10 via the reaction vessel 3 , the reaction solution 2 , and so on, then the charge separation occurs by the light energy.
  • the positive holes generated by the charge separation move toward the oxidation electrode 11 , and the electrons move toward the reduction electrode 21 .
  • the oxidation reaction of H 2 O occurs based on the above-stated (6) expression to generate O 2 and H + in the vicinity of the oxidation catalyst layer 12 provided on the oxidation electrode 11 toward which the positive holes move.
  • the reduction reactions of the intermediate substance and CO 2 occur based on the above-stated (7) expression, (8) expression, (9) expression and so on, and the carbon compounds such as CO are generated in the vicinity of the reduction catalyst layer 22 provided on the reduction electrode 21 toward which the electrons move.
  • Gaseous products containing O 2 generated by the oxidation reaction of H 2 O, and the carbon compound (CO and so on) generated by the reduction reaction of the intermediate substance and CO 2 are collected at the upper space S of the reaction vessel 3 , and thereafter, transferred to the product collection part 107 via the product send-out pipe 7 e.
  • the generated O 2 and carbon compounds may be supplied to incinerators of, for example, a power station, an ironwork, a chemical factory, a garbage incineration plant, and so on as a carbon fuel containing a combustion improver. It is also possible to separate O 2 and the carbon compounds to be individually used.
  • a part or all of the reaction solution 2 in which the reaction finishes is refluxed to the CO 2 conversion part 102 via the reaction solution lead-out pipe 7 c.
  • the reaction solution 2 refluxed to the CO 2 conversion part 102 is reused at the CO 2 conversion part 102 .
  • a part of the reaction solution 2 after the reaction is discharged out of the system via the reaction solution discharge pipe 7 d according
  • CO 2 is converted into at least one intermediate substance selected from the metal carbonate and the metal hydrogen carbonate by the metal hydroxide, and the aqueous solution containing the intermediate substance (a solution containing the intermediate substance and H 2 O) is used as the reaction solution instead of absorbing CO 2 by amine molecules which are easy to be oxidized and an expensive ionic liquid.
  • the reaction solution as stated above is used, and thereby, it is possible to apply the one-liquid type reaction vessel 3 , and to simplify the electrode structure and the cell structure. The cost reduction, small-sizing, and so on of the device of the CO 2 reduction part 104 become possible.
  • the reaction solution is alkaline, and therefore, it is possible to increase the oxidation reaction efficiency of H 2 O. Accordingly, it becomes possible to provide the inexpensive and small-sized photoelectrochemical reaction system 100 which is excellent in the reaction efficiency as a whole of the oxidation-reduction reaction.
  • FIG. 10 is a configuration chart of a photoelectrochemical reaction system according to a second embodiment.
  • a photoelectrochemical reaction system 110 of the second embodiment includes the CO 2 conversion part 102 , the reaction solution transfer part 103 , a first CO 2 reduction part 104 A, a first reaction solution adjustment part 105 A, a first reaction solution reflux part 106 A, a second CO 2 reduction part 104 B, a second reaction solution adjustment part 105 B, a second reaction solution reflux part 106 B, and the product collection part 107 .
  • the photoelectrochemical reaction system 110 of the second embodiment is provided subsidiary to the CO 2 generation part 100 X.
  • the photoelectrochemical reaction system 110 may include an impurity removal part 101 in the same way as the first embodiment.
  • the photoelectrochemical reaction system 110 of the second embodiment includes the CO 2 reduction part 104 , reaction solution adjustment part 105 , and reaction solution reflux part 106 in two systems relative to the CO 2 generation part 100 X, CO 2 conversion part 102 , and reaction solution transfer part 103 in one system.
  • the other configurations are the same as the photoelectrochemical reaction system 100 of the first embodiment.
  • Detailed configurations of respective parts 100 X, 102 , 103 , 104 , 105 , 106 , 107 are the same as the photoelectrochemical reaction system 100 of the first embodiment.
  • the photoelectrochemical reaction system 110 may include a reaction solution storage part.
  • One of the system including the CO 2 conversion part 102 and the system including the CO 2 reduction part 104 can be made to be plural systems depending on processing capabilities of the CO 2 conversion part 102 and the CO 2 reduction part 104 .
  • FIG. 10 is an example of a case when the processing capability of the CO 2 conversion part 102 is superior to the processing capability of the CO 2 reduction part 104 .
  • the system including the CO 2 reduction part 104 is made to be the plural systems relative to the system including the CO 2 conversion part 102 , and thereby, it is possible to efficiently operate the CO 2 conversion part 102 .
  • This contributes to improvement in the process efficiency as a whole of the photoelectrochemical reaction system 110 .
  • the system including the CO 2 conversion part 102 can be made to be the plural systems relative to the system including the CO 2 reduction part 104 .
  • the other effects are the same as the first embodiment.

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JP6631467B2 (ja) * 2016-10-31 2020-01-15 株式会社デンソー 二酸化炭素還元装置
KR102153734B1 (ko) * 2018-05-04 2020-09-08 울산과학기술원 광전극, 이의 제조방법 및 이를 이용한 광전기화학적 물분해 방법

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US20120277465A1 (en) * 2010-07-29 2012-11-01 Liquid Light, Inc. Reduction of carbon dioxide to carboxylic acids, glycols, and carboxylates
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