WO2015146008A1 - Système de réaction photoélectrochimique - Google Patents

Système de réaction photoélectrochimique Download PDF

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Publication number
WO2015146008A1
WO2015146008A1 PCT/JP2015/001205 JP2015001205W WO2015146008A1 WO 2015146008 A1 WO2015146008 A1 WO 2015146008A1 JP 2015001205 W JP2015001205 W JP 2015001205W WO 2015146008 A1 WO2015146008 A1 WO 2015146008A1
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reaction
reduction
electrode
unit
photoelectrochemical
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PCT/JP2015/001205
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English (en)
Japanese (ja)
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静君 黄
御子柴　智
昭彦 小野
良太 北川
由紀 工藤
田村　淳
栄史 堤
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株式会社 東芝
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Priority to JP2016509970A priority Critical patent/JP6258467B2/ja
Publication of WO2015146008A1 publication Critical patent/WO2015146008A1/fr
Priority to US15/247,178 priority patent/US20160362801A1/en

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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
    • 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
    • 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
    • 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
    • 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 of the present invention relate to photoelectrochemical reaction systems.
  • Plants use a system that is excited in two steps by light energy called a Z scheme. That is, a plant obtains electrons from water (H 2 O) by light energy and synthesizes cellulose and saccharides by reducing carbon dioxide (CO 2 ) using the electrons.
  • a Z scheme As an apparatus for artificial photosynthesis, development of a photoelectrochemical reaction apparatus for reducing (decomposing) CO 2 with light energy is in progress.
  • the artificial photoelectrochemical reaction device includes an electrode having a reduction catalyst for reducing carbon dioxide (CO 2 ) and an electrode having an oxidation catalyst for oxidizing water (H 2 O), and these electrodes are CO 2
  • CO 2 carbon dioxide
  • H 2 O oxidation catalyst for oxidizing water
  • a two-electrode system device in which water is immersed in dissolved water. When water is used as the electrolytic solution, the CO 2 decomposition efficiency can not be enhanced because the dissolved concentration of CO 2 is low.
  • a photoelectrochemical reaction device that decomposes water (H 2 O) with light energy to obtain oxygen (O 2 ) and hydrogen (H 2 ) a laminate in which a photovoltaic layer is sandwiched between a pair of electrodes is used Is being considered.
  • an aqueous solution containing an amine molecule, an ionic liquid, etc. have been studied.
  • an alkaline aqueous solution such as an aqueous potassium hydroxide solution or an aqueous sodium hydroxide solution or an aqueous amine solution is used as an electrolytic solution in a conventional CO 2 reduction device (CO 2 electrolysis device).
  • an aqueous amine solution used as a CO 2 absorbent has low chemical stability and is gradually oxidized even in a natural state. Since the oxidation electrode side of the photoelectrochemical reactor is a strong oxidizing environment, amine molecules in the aqueous solution are preferentially oxidized, and the aqueous amine solution can not be recovered or reused. For this reason, in the conventional photoelectrochemical reaction apparatus, the inside of the electrolytic cell is isolated to the oxidation electrode side and the reduction electrode side, but this causes the cell structure to be complicated and the like, which increases the apparatus cost, and further the apparatus Is easy to enlarge.
  • the ionic liquid is chemically stable, itself is expensive, which causes an increase in the cost of the apparatus.
  • the transportability and transport efficiency of CO 2 from the device that discharges CO 2 to the electrolyzer are not considered, and the configuration as a photoelectrochemical reaction system is not constructed.
  • the problem to be solved by the present invention is to provide a photoelectrochemical reaction system in which the efficiency of decomposition of CO 2 by light energy is enhanced and the efficiency of the entire system is improved.
  • the photoelectrochemical reaction system of the embodiment converts carbon dioxide into at least one intermediate substance selected from the group consisting of metal carbonates and metal hydrogencarbonates by an aqueous solution containing a metal hydroxide, and a reaction containing the intermediate substance
  • a conversion unit that generates a solution, a transfer unit that transfers a reaction solution containing an intermediate substance, a one-component reaction tank in which the reaction solution is introduced by the transfer unit, and an oxidation electrode that is immersed in the reaction solution to oxidize water
  • a reduction electrode which is immersed in the reaction solution and reduces the intermediate substance, and a photovoltaic element electrically connected to the oxidation electrode and the reduction electrode and performing charge separation by light energy.
  • FIG. 1st Embodiment It is a block diagram of the photoelectrochemical reaction system by 1st Embodiment. It is a figure which shows the 1st example of the photoelectrochemical module used for the photoelectrochemical reaction system shown in FIG. It is a figure which shows the 2nd example of the photoelectrochemical module used for the photoelectrochemical reaction system shown in FIG. It is a figure which shows the oxidation electrode used for the photoelectrochemical module shown in FIG. It is a figure which shows the reduction electrode used for the photoelectrochemical module shown in FIG. It is a figure which shows the photovoltaic device used for the photoelectrochemical module shown in FIG.
  • FIG. 1 is a view showing the configuration of a photoelectrochemical reaction system according to a first embodiment.
  • the photoelectrochemical reaction system 100 of the first embodiment is installed in addition to the CO 2 generation unit 100X that generates a gas containing carbon dioxide (CO 2 ).
  • the photoelectrochemical reaction system 100 includes a CO 2 conversion unit 102, a reaction solution transfer unit 103, a CO 2 reduction unit 104, a reaction solution adjustment unit 105, a reaction solution reflux unit 106, a product collection unit 107, and a reaction solution storage unit 108. Equipped with A power plant can be mentioned as a representative example of the CO 2 generation unit 100X.
  • the CO 2 generation unit 100X is not limited to this, and may be an iron factory, a chemical plant, a waste incineration site, or the like.
  • the CO2 generation unit 100X is not particularly limited.
  • the photoelectrochemical reaction system 100 according to the embodiment can reduce the size and the like of the CO 2 reducing unit 104 as described later, and is not limited to large plants such as a power plant and an iron factory, but may be a waste incineration site. It is also effective for small plants.
  • a gas containing CO 2 generated in the CO 2 generation unit 100 X for example, an exhaust gas discharged from a power plant, an iron factory, a chemical plant, a waste incineration plant or the like is sent to the CO 2 conversion unit 102 of the photoelectrochemical reaction system 100.
  • the impurities such as sulfur oxide in the exhaust gas may be removed and then sent to the CO 2 conversion unit 102.
  • the photoelectrochemical reaction system 100 may include the impurity removing unit 101.
  • the impurity removal unit 101 is not limited to between the CO 2 generation unit 100 X and the CO 2 conversion unit 102, and may be anywhere in the CO 2 circulation path.
  • the CO 2 conversion unit 102, the reaction solution transfer unit 103, It may be between any of the CO 2 reduction unit 104, the reaction solution reflux unit 106, and the reaction solution storage unit 108.
  • impurities not only components in the exhaust gas but also decomposition products of piping and reaction solution, chemically changed substances, substances eluted from piping and tank by reaction solution, metal ions from CO 2 reduction section 104, etc. are considered.
  • the impurity removing unit 101 may be a dry or wet gas processing apparatus, an ion exchange resin that absorbs metal ions, a filter that removes sulfur oxides or nitrogen oxides, physical decomposition products such as piping, tanks, and a stirrer. The filter to remove is mentioned.
  • CO 2 is converted to at least one intermediate selected from metal carbonates and metal hydrogen carbonates.
  • the CO 2 conversion unit 102 has a reaction vessel containing an aqueous solution containing a metal hydroxide that converts CO 2 into an intermediate substance.
  • a gas containing CO 2 is blown into the reaction vessel containing the aqueous solution of metal hydroxide by a gas supply pipe.
  • the CO 2 blown into the aqueous solution is converted by the metal hydroxide to at least one intermediate selected from metal carbonates and metal hydrogencarbonates.
  • a reaction solution (aqueous solution) containing the intermediate is generated in the reaction vessel. That is, the CO 2 conversion unit 102 generates a reaction solution (aqueous solution) containing water (H 2 O) and at least one intermediate substance selected from metal carbonates and metal hydrogencarbonates.
  • the metal hydroxide that converts CO 2 into an intermediate is preferably a hydroxide of at least one metal selected from an alkali metal (Group 1 element) and an alkaline earth metal (Group 2 element).
  • the metal hydroxide is at least selected from lithium (Li), sodium (Na), potassium (K), rubidium (Rb), beryllium (Be), magnesium (Mg), calcium (Ca), and strontium (Sr) More preferably, it is a hydroxide of one metal.
  • the pH of the aqueous solution containing the metal hydroxide is preferably adjusted to a range of 7-14.
  • the pH of the aqueous solution containing the metal hydroxide In order to enhance the reactivity between CO 2 and the metal hydroxide, it is preferable to adjust the pH of the aqueous solution containing the metal hydroxide to a strongly alkaline region. On the other hand, in order to suppress corrosion of components such as the CO 2 conversion unit 102 and the CO 2 reduction unit 104, it is preferable to adjust the pH of the aqueous solution containing the metal hydroxide to a weakly alkaline region.
  • CO 2 is represented by the following formula (4) or (5) Converted to calcium carbonate or calcium hydrogen carbonate based on.
  • the other alkaline earth metals (group 2 elements) are almost the same.
  • the reaction solution (aqueous solution) containing the intermediate substance (metal carbonate or metal bicarbonate) generated in the CO 2 conversion unit 102 is sent to the CO 2 reduction unit 104 by the reaction solution transfer unit 103.
  • the CO 2 conversion unit 102 and the CO 2 reduction unit 104 do not have to be operated at the same time.
  • the reaction solution containing the intermediate substance generated by the CO 2 conversion unit 102 is a reaction solution It is stored in the storage unit 108.
  • the reaction solution stored in the reaction solution reservoir 108 is sent to the CO 2 reduction unit 104 during the operation of the CO 2 reduction unit 104.
  • the CO 2 reduction unit 104 includes the photoelectrochemical module 1 shown in FIGS. 2 and 3.
  • FIG. 2 shows a photoelectrochemical module 1A in which the photovoltaic element is disposed outside the reaction solution and the oxidation electrode and the reduction electrode are immersed in the reaction solution.
  • FIG. 3 shows a photoelectrochemical module 1B in which a laminate (photoelectrochemical cell) of an oxidation electrode, a photovoltaic layer and a reduction electrode is immersed in a reaction solution.
  • the photoelectrochemical module 1A (104) shown in FIG. 2 comprises a one-pack type reaction tank 3 containing the reaction solution 2, an oxidation electrode 4 and a reduction electrode 5 immersed in the reaction solution 2, and A photovoltaic element 6 disposed outside and electrically connected to the oxidation electrode 4 and the reduction electrode 5 is provided.
  • the reaction solution introduction pipe 7a for introducing the reaction solution 2 by the reaction solution transfer unit 103, the adjustment liquid introduction pipe 7b for introducing the adjustment solution of the reaction solution 2 from the reaction solution adjustment unit 105, and the reaction solution reflux unit 106 Connects the reaction solution discharge pipe 7c for discharging the solution after reaction, the reaction solution discharge pipe 7d for discharging the solution after reaction, and the product delivery pipe 7e for delivering gaseous reaction products to the product collection unit 107. It is done.
  • the reaction solution containing the intermediate substance generated by the CO 2 conversion unit 102 is introduced through the reaction solution introduction pipe 7a.
  • the introduction amount of the reaction solution is adjusted so that a predetermined space S is generated in the upper part of the reaction tank 3. Gaseous products generated by the oxidation-reduction reaction in the reaction tank 3 are collected in the upper space S of the reaction tank 3 and then sent to the product collection unit 107 via the product delivery pipe 7e.
  • An adjusting liquid is further introduced into the reaction tank 3 through the adjusting liquid introduction pipe 7b as necessary.
  • the reaction solution in the reaction tank 3 is adjusted with the adjusting liquid so as to have a desired concentration, properties and the like.
  • reaction solution in which the redox reaction has been performed in the reaction tank 3 is refluxed to the CO 2 converter 102 through the reaction solution discharge pipe 7 c.
  • a part of the reaction solution after the reaction is discharged out of the system through the reaction solution discharge pipe 7d as necessary.
  • the introduction and discharge of the reaction solution may be carried out continuously or batchwise at discrete times.
  • the reaction tank 3 is preferably formed of a material which does not react chemically with the reaction solution 2 and which is difficult to deteriorate by the energy of sunlight.
  • materials for example, polyetheretherketone (PEEK) resin, polyamide (PA) resin, polyvinylidene fluoride (PVDF) resin, polyacetal (POM) resin (copolymer), polyphenylene ether (PPE) resin, acrylonitrile-butadiene -Resin materials such as styrene copolymer (ABS), polypropylene (PP) resin, polyethylene (PE) resin and the like can be mentioned.
  • PEEK polyetheretherketone
  • PA polyamide
  • PVDF polyvinylidene fluoride
  • POM polyacetal
  • PPE polyphenylene ether
  • ABS styrene copolymer
  • PP polyprop
  • the reaction tank 3 may be provided with a stirrer for stirring the reaction solution 2.
  • the upper space S of the reaction vessel 3 is preferably completely sealed except for the product delivery pipe 7e in order to efficiently collect and discharge the gas product.
  • the reaction solution 2 introduced into the reaction tank 3 is adjusted by the reaction solution adjusting unit 105 so as to have a concentration and properties suitable for the oxidation reaction of H 2 O and the reduction reaction of the intermediate substance.
  • an aqueous solution of the same metal hydroxide as water or the CO 2 conversion unit 102 is added via the adjustment liquid introduction pipe 7 b so that the pH of the reaction solution 2 is in the range of 10.0 to 14.0. It is preferable to introduce it into the reaction tank 3.
  • a redox couple may be added to the reaction solution 2. Examples of the redox couple include Fe 3+ / Fe 2+ and IO 3 ⁇ / I ⁇ .
  • the oxidation electrode 4 and the reduction electrode 5 are disposed so as to be immersed in the reaction solution 2.
  • the oxidation electrode 4 has an oxidation catalyst layer 8 formed on both sides of the supporting substrate 4a.
  • the support base 4 a of the oxidation electrode 4 is formed of a material having conductivity. Examples of the forming material of the supporting base 4 a include metals such as Cu, Al, Ti, Ni, Fe, Ag, an alloy containing at least one of these metals, and a conductive resin.
  • a metal plate or an alloy plate is used in consideration of the formability of the oxidation catalyst layer 8.
  • the support substrate 4a may be made of a porous material such as a metal, an alloy, or a conductive resin.
  • the oxidation catalyst layer 8 has a function of receiving holes from the supporting substrate 4 a of the oxidation electrode 4 and reacting with H 2 O in the reaction solution 2 to oxidize H 2 O.
  • the constituent material of the oxidation catalyst layer 8 preferably contains an oxide or hydroxide of at least one metal selected from Fe, Ni, Co, Cu, Ti, V, Mn, Ru, and Ir.
  • Specific materials of the oxidation catalyst layer 8 include RuO 2 , NiO, Ni (OH) 2 , NiOOH, Co 3 O 4 , Co (OH) 2 , CoOOH, FeO, Fe 2 O 3 , MnO 2 , and Mn.
  • One or more composite materials selected from 3 O 4 , Rh 2 O 3 , and IrO 2 can be mentioned.
  • the oxidation catalyst layer 8 promotes the oxidation reaction of H 2 O in the oxidation electrode 4, the oxidation catalyst layer 8 can be omitted if the reaction rate of the oxidation reaction by the supporting substrate 4 a of the oxidation electrode 4 is sufficient.
  • the reduction electrode 5 has a support base 5a and a reduction catalyst layer 9 formed on both sides thereof.
  • the support substrate 5 a of the reduction electrode 5 is formed of a material having conductivity.
  • the forming material of the supporting base 5a include metals such as Cu, Al, Ti, Ni, Fe, Ag, an alloy containing at least one of these metals, and a conductive resin.
  • a metal plate or an alloy plate is used in consideration of the formability of the reduction catalyst layer 9.
  • the support substrate 5a may be made of a porous body of metal, alloy, conductive resin or the like.
  • the reduction catalyst layer 9 has a function of receiving electrons from the supporting substrate 5 a of the reduction electrode 5 and reducing an intermediate substance in the reaction solution 2, that is, metal carbonate and metal hydrogen carbonate, and CO 2 generated thereby.
  • the constituent material of the reduction catalyst layer 9 is a metal such as Au, Ag, Zn, Cu, Hg, Cd, Pb, Ti, In, Sn, a metal complex such as a ruthenium complex or rhenium complex, graphene, CNT (carbon nanotube) It is preferable to contain carbon materials such as fullerene, ketjen black and the like. Since the reduction catalyst layer 9 promotes the reduction reaction of CO 2 in the reduction electrode 5, the reduction catalyst layer 9 can be omitted if the reaction rate of the reduction reaction by the support substrate 5 a of the reduction electrode 5 is sufficient.
  • the photovoltaic element 6 is electrically connected to the oxidation electrode 4 and the reduction electrode 5, thereby exchanging electrons and holes with the oxidation electrode 4 and the reduction electrode 5.
  • the photovoltaic element 6 performs charge separation by light energy.
  • the photovoltaic element 6 needs to create a potential difference higher than the difference between the standard redox potential of the oxidation reaction of H 2 O generated near the oxidation electrode 4 and the standard redox potential of the reduction reaction of CO 2 generated near the reduction electrode 5 There is. That is, the photovoltaic element 6 can provide the energy necessary for simultaneously causing the oxidation reaction of H 2 O and the reduction reaction of CO 2 .
  • the photovoltaic element 6 includes the first electrode layer 11, the photovoltaic layer 31, and the second electrode layer 21.
  • FIG. 7 shows a specific example of the photovoltaic element 6 using a silicon solar cell (pin junction) as the photovoltaic layer 31.
  • the second electrode layer 21 is formed of a metal such as Cu, Al, Ti, Ni, Fe, Ag, an alloy such as SUS containing at least one of these metals, a conductive resin, a semiconductor such as Si or Ge, or the like. Ru.
  • a metal plate, an alloy plate, a resin plate, a semiconductor substrate or the like is used for the second electrode layer 21, a metal plate, an alloy plate, a resin plate, a semiconductor substrate or the like is used.
  • the photovoltaic layer 31 is formed on the second electrode layer 21.
  • the photovoltaic layer 31 is composed of the reflective layer 32, the first photovoltaic layer 33, the second photovoltaic layer 34, and the third photovoltaic layer 35.
  • the reflective layer 32 is formed on the second electrode layer 21 and has a first reflective layer 32a and a second reflective layer 32b formed in order from the lower side.
  • a metal such as Ag, Au, Al, Cu, etc., which has light reflectivity and conductivity, an alloy containing at least one of these metals, or the like is used.
  • the second reflective layer 32 b is provided to adjust the optical distance to enhance the light reflectivity.
  • the second reflective layer 32 b is preferably made of a material having optical transparency and capable of making ohmic contact with the n-type semiconductor layer because the second reflective layer 32 b is joined to the n-type semiconductor layer of the photovoltaic layer 31 described later.
  • transparent conductive oxide such as ITO (indium tin oxide), zinc oxide (ZnO), FTO (fluorine-doped tin oxide), AZO (aluminum-doped zinc oxide), ATO (antimony-doped tin oxide), etc. The thing is used.
  • the first photovoltaic layer 33, the second photovoltaic layer 34, and the third photovoltaic layer 35 are each a solar cell using a pin junction semiconductor, and they have different light absorption wavelengths. By laminating these layers in a planar manner, the photovoltaic layer 31 can absorb light of a wide wavelength of sunlight, and energy of the sunlight can be efficiently used. Since the photovoltaic layers 33, 34, 35 are connected in series, a high open circuit voltage can be obtained.
  • the first photovoltaic layer 33 is formed on the reflective layer 32, and an n-type amorphous silicon (a-Si) layer 33a formed in order from the lower side, intrinsic amorphous silicon germanium (a-) And a p-type microcrystalline silicon (mc-Si) layer 33c.
  • the a-SiGe layer 33 b is a layer that absorbs light in a long wavelength region of about 700 nm. In the first photovoltaic layer 33, charge separation occurs due to light energy in the long wavelength region.
  • the second photovoltaic layer 34 is formed on the first photovoltaic layer 33, and an n-type a-Si layer 34a, an intrinsic a-SiGe layer 34b, which are sequentially formed from the lower side, And a p-type mc-Si layer 34c.
  • the a-SiGe layer 34 b is a layer that absorbs light in an intermediate wavelength region of about 600 nm. In the second photovoltaic layer 34, charge separation occurs by light energy in the intermediate wavelength region.
  • the third photovoltaic layer 35 is formed on the second photovoltaic layer 34, and is an n-type a-Si layer 35a, an intrinsic a-Si layer 35b, formed sequentially from the lower side, And a p-type mc-Si layer 35c.
  • the a-Si layer 35b is a layer that absorbs light in a short wavelength region of about 400 nm. In the third photovoltaic layer 35, charge separation occurs due to light energy in the short wavelength region.
  • the first electrode layer 11 is formed on the p-type semiconductor layer (p-type mc-Si layer 35 c) of the photovoltaic layer 31.
  • the first electrode layer 11 is preferably formed of a material capable of ohmic contact with the p-type semiconductor layer.
  • a metal such as Ag, Au, Al or Cu, an alloy containing at least one of these metals, a transparent conductive oxide such as ITO, ZnO, FTO, AZO, ATO or the like is used.
  • the first electrode layer 11 has, for example, a structure in which a metal and a transparent conductive oxide are laminated, a structure in which a metal and another conductive material are composited, and a transparent conductive oxide and another conductive material are composited It may have the same structure or the like.
  • the irradiation light passes through the first electrode layer 11 and reaches the photovoltaic layer 31.
  • the first electrode layer 11 has optical transparency to the irradiation light.
  • charge separation occurs due to the energy of the light of each wavelength region of the irradiation light (sunlight etc.).
  • an electromotive force is generated in the photovoltaic layer 31 by separating holes toward the first electrode layer 11 and electrons toward the second electrode layer 21. Therefore, the first electrode layer 11 to which holes move is electrically connected to the oxidation electrode 4, and the second electrode layer 21 to which electrons move is electrically connected to the reduction electrode 5.
  • FIG. 7 illustrates the photovoltaic layer 31 having a stacked structure of three photovoltaic layers as an example, the photovoltaic layer 31 is not limited to this.
  • the photovoltaic layer 31 may have a laminated structure of two or four or more photovoltaic layers. Instead of the photovoltaic layer 31 of the laminated structure, one photovoltaic layer 31 may be used.
  • the photovoltaic layer 31 is not limited to a solar cell using a pin junction type semiconductor, and may be a solar cell using a pn junction type semiconductor.
  • the semiconductor layer is not limited to Si or Ge, and may be a compound semiconductor such as GaAs, GaInP, AlGaInP, CdTe, CuInGaSe or the like.
  • FIG. 7 illustrates the photovoltaic layer 31 having a stacked structure of three photovoltaic layers as an example, the photovoltaic layer 31 is not limited to this.
  • the photovoltaic layer 31 may have a laminated structure of two or four or
  • the photovoltaic device 6 is not limited to a silicon solar cell, and another solar cell may be applied.
  • the light irradiation side is not limited to the p-type semiconductor layer, and may be an n-type semiconductor layer.
  • sodium hydrogen carbonate (NaHCO 3 ) will be described as a representative example of the intermediate substance, but the same applies to other metal carbonates and metal hydrogen carbonates.
  • NaHCO 3 sodium hydrogen carbonate
  • An oxidation reaction of H 2 O occurs in the vicinity of the oxidation electrode 4 from which the holes move.
  • the holes transferred to the oxidation electrode 4 combine with the electrons generated by the oxidation reaction.
  • a reduction reaction of intermediates and CO 2 occurs.
  • the electrons transferred to the reduction electrode 5 are used for the reduction reaction.
  • CO 2 is generated from a metal carbonate or metal hydrogen carbonate as an intermediate substance.
  • the CO 2 generated by the reaction of the metal carbonate or the metal hydrogencarbonate is reduced in the vicinity of the reduction electrode 5 (to obtain electrons).
  • CO 2 produced by the reaction of metal carbonates and metal hydrogen carbonates are produced by the oxidation electrode 4 side, the H + which has moved to the reduction electrode 5 side by diffusing the reaction solution 2, light It is generated by the charge separation in the electromotive force element 6 and reacts with the electrons transferred to the reduction electrode 5 to generate, for example, CO and H 2 O.
  • the reactions of the formulas (7) to (9) are an example of the reaction in the vicinity of the reduction electrode 5, and metal carbonates and metal hydrogencarbonates are directly reduced to produce CO and H 2 O. It may be generated.
  • metal carbonates and metal hydrogencarbonates are directly reduced to produce CO and H 2 O. It may be generated.
  • the photoelectrochemical module 1B (104) shown in FIG. 3 includes a one-pack type reaction tank 3 containing the reaction solution 2 and a photoelectrochemical cell immersed in the reaction solution 2, that is, an oxidation catalyst layer 12, an oxidation electrode A laminate 10 of a (first electrode) 11, a photovoltaic layer 31, a reduction electrode (second electrode) 21, and a reduction catalyst layer 22 is provided. According to the photoelectrochemical module 1B, simplification of the constituent elements can be achieved as compared to the photoelectrochemical module 1A shown in FIG.
  • the reaction tank 3 in the photoelectrochemical module 1B (104) has the same configuration (each piping, etc.) as the reaction tank 3 of the photoelectrochemical module 1A shown in FIG.
  • the reaction vessel 3 does not react chemically with the reaction solution 2 and is a material that transmits light, ie, 250 ⁇ It is made of a material having a low absorptivity of light in the wavelength region of 1100 nm.
  • Examples of materials for forming such a reaction vessel 3 include quartz, white sheet glass, polystyrene and methacrylate. Only the window for light irradiation may be formed of the above-described material, and the other portion may be the reaction tank 3 formed of the above-described resin material.
  • the oxidation catalyst layer 12 is formed on the first electrode (oxidation electrode) 11 of the photovoltaic element 6 shown in FIG. 7, and the second electrode (reduction electrode)
  • the structure which formed the reduction catalyst layer 22 on 21 is mentioned.
  • the catalyst layer disposed on the light irradiation side has light transparency.
  • the configuration of the photoelectrochemical cell 10 is not limited to this, and a pin junction having an oxidation catalyst layer and a reduction catalyst layer, a pn junction, an amorphous silicon solar cell, a multijunction solar cell, a single crystal silicon solar cell, many A crystalline silicon solar cell, a dye-sensitized solar cell, an organic thin film solar cell or the like can be applied.
  • the photoelectrochemical cell 10 needs to create a potential difference higher than the difference between the standard redox potential of the oxidation reaction of H 2 O generated near the oxidation electrode 11 and the standard redox potential of the reduction reaction of CO 2 generated near the reduction electrode 21. There is. That is, the photoelectrochemical cell 10 can provide the energy necessary for simultaneously causing the oxidation reaction of H 2 O and the reduction reaction of CO 2 .
  • 50% or more of light energy passes through the reaction vessel 3, the reaction solution 2, and the oxidation catalyst layer 12 from the outside of the reaction vessel 3. It is preferable to be configured to reach the electromotive force layer 31.
  • metals such as Ag, Au, Al and Cu, alloys containing at least one of these metals, and transparent such as ITO, ZnO, FTO, AZO, ATO A conductive oxide etc. are mentioned.
  • the oxidation electrode 11 of the photoelectrochemical cell 10 has been described as the light irradiation side, the present invention is not limited to this, and the reduction electrode 21 may be on the light irradiation side.
  • the constituent materials of the oxidation catalyst layer 12 and the reduction catalyst layer 22 are as described above.
  • the catalyst layer disposed on the light irradiation side of the oxidation catalyst layer 12 and the reduction catalyst layer 22 and the electrode disposed on the light irradiation side of the oxidation electrode 11 and the reduction electrode 21 have light transparency.
  • the photoelectrochemical cell 10 may be a laminate in which the oxidation catalyst layer 12, the oxidation electrode 11, the photovoltaic layer 31, the reduction electrode 21, and the reduction catalyst layer 22 are simply integrated, or such a laminate Alternatively, through holes may be formed in the stacking direction as ion passing holes. In order to transfer H + ions and the like efficiently between the oxidation reaction and the reduction reaction, it is preferable to provide a through hole in the photoelectrochemical cell 10, whereby the reaction efficiency is improved.
  • the through holes are provided to penetrate from the oxidation catalyst layer 12 which is one surface layer of the photoelectrochemical cell 10 to the reduction catalyst layer 22 which is the other surface layer.
  • the reduction reaction of the intermediate substance or CO 2 is performed based on the above-mentioned equations (7), (8), (9), etc. Occurs to form a carbon compound such as CO.
  • Gaseous products containing O 2 and intermediates produced by the oxidation reaction of H 2 O and carbon compounds (such as CO) produced by the reduction reaction of CO 2 were collected in the upper space S of the reaction vessel 3 Thereafter, it is sent to the product collection unit 107 via the product delivery pipe 7e.
  • the generated O 2 or carbon compound may be supplied, for example, as a carbon fuel containing a flame retardant to a combustion furnace such as a power plant, an iron factory, a chemical plant, or a waste disposal site. O 2 and carbon compounds can be separated and used individually.
  • Part or all of the reaction solution 2 in which the reaction is completed is refluxed to the CO 2 converter 102 through the reaction solution discharge pipe 7 c.
  • the reaction solution 2 was refluxed in CO 2 conversion unit 102 is reused in CO 2 conversion unit 102. A part of the reaction solution 2 after the reaction is discharged out of the system through the reaction solution discharge pipe 7d as necessary.
  • metal carbonate and metal hydrogen carbonate using CO 2 are metal hydroxides.
  • An aqueous solution containing an intermediate (a solution containing an intermediate and H 2 O) is used as a reaction solution after conversion into at least one intermediate selected from salts.
  • the reaction solution is alkaline, the oxidation reaction efficiency of H 2 O can be enhanced. Therefore, it is possible to provide the photoelectrochemical reaction system 100 which is excellent in reaction efficiency as a whole of the redox reaction, and is inexpensive and compact.
  • FIG. 10 is a block diagram of a photoelectrochemical reaction system according to a second embodiment.
  • the photoelectrochemical reaction system 110 according to the second embodiment includes a CO 2 conversion unit 102, a reaction solution transfer unit 103, a first CO 2 reduction unit 104A, a first reaction solution adjustment unit 105A, a first reaction solution reflux unit 106A, a first A 2CO 2 reduction unit 104B, a second reaction solution adjustment unit 105B, a second reaction solution reflux unit 106B, and a product collection unit 107 are provided.
  • the photoelectrochemical reaction system 110 of the second embodiment is installed in association with the CO 2 generation unit 100X.
  • the photoelectrochemical reaction system 110 may include the impurity removing unit 101 as in the first embodiment.
  • the photoelectrochemical reaction system 110 includes two systems of CO 2 reduction units 104 and reaction solution adjustment with respect to one system of CO 2 generation unit 100 X, CO 2 conversion unit 102, and reaction solution transfer unit 103. A portion 105 and a reaction solution reflux portion 106 are provided.
  • the other configuration is the same as that of the photoelectrochemical reaction system 100 of the first embodiment.
  • the detailed configuration of each part 101, 102, 103, 104, 105, 106, 107 is also the same as that of the photoelectrochemical reaction system 100 of the first embodiment.
  • the photoelectrochemical reaction system 110 may include a reaction solution storage unit.
  • the processing capability of CO 2 conversion unit 102 and the CO 2 reduction unit 104 can be one of a plurality of systems of systems including system and CO 2 reduction unit 104 including a CO 2 conversion unit 102.
  • FIG. 10 shows an example of the case where the processing capacity of the CO 2 conversion unit 102 is superior to the processing capacity of the CO 2 reduction unit 104.
  • the CO 2 conversion unit 102 can be operated efficiently by providing a plurality of systems including the CO 2 reduction unit 104 with respect to the system including the CO 2 conversion unit 102. This contributes to the improvement of the processing efficiency of the photoelectrochemical reaction system 110 as a whole.
  • first and second embodiments can be combined and applied, and can be partially replaced. While certain embodiments of the present invention have been described herein, these embodiments have been presented by way of example only, and are not intended to limit the scope of the invention. These embodiments can be implemented in other various forms, and various omissions, replacements, and modifications can be made without departing from the scope of the invention. These embodiments and modifications thereof are included in the scope and the gist of the invention, and at the same time, included in the invention described in the claims and the equivalents thereof.

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Abstract

L'invention concerne un système de réaction photoélectrochimique (100) pourvu d'une unité de conversion de CO2 (102) et d'une unité de réduction de CO2 (104). L'unité de conversion de CO2 (102) convertit le CO2 en au moins un intermédiaire sélectionné parmi les carbonates de métal et les hydrogénocarbonates de métal au moyen d'une solution aqueuse contenant un hydroxyde de métal, et produit une solution de réaction contenant l'intermédiaire. L'unité de réduction de CO2 (104) est pourvue : d'une cuve de réaction de type à un compartiment dans laquelle la solution de réaction contenant l'intermédiaire est introduite ; d'une électrode d'oxydation et d'une électrode de réduction, qui sont immergées dans la solution de réaction; et d'un élément photovoltaïque qui est connecté électriquement à l'électrode d'oxydation et à l'électrode de réduction. Par conséquent, de l'O2 est produit au voisinage de l'électrode d'oxydation en oxydant de l' H2O, et un composé de carbone est produit au voisinage de l'électrode de réduction par réduction de l'intermédiaire.
PCT/JP2015/001205 2014-03-24 2015-03-05 Système de réaction photoélectrochimique WO2015146008A1 (fr)

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KR20190127405A (ko) * 2018-05-04 2019-11-13 울산과학기술원 광전극, 이의 제조방법 및 이를 이용한 광전기화학적 물분해 방법

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JP2005146296A (ja) * 2003-11-11 2005-06-09 Permelec Electrode Ltd 過炭酸の製造方法
JP2012505310A (ja) * 2008-10-08 2012-03-01 マサチューセッツ インスティテュート オブ テクノロジー 触媒材料、光アノード、ならびに水電気分解およびたの電気化学技術のための光電気化学セル

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KR20190127405A (ko) * 2018-05-04 2019-11-13 울산과학기술원 광전극, 이의 제조방법 및 이를 이용한 광전기화학적 물분해 방법
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