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WO2015151775A1 - Photoélectrode à utiliser dans la décomposition d'eau, et dispositif de décomposition d'eau - Google Patents

Photoélectrode à utiliser dans la décomposition d'eau, et dispositif de décomposition d'eau Download PDF

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Publication number
WO2015151775A1
WO2015151775A1 PCT/JP2015/057714 JP2015057714W WO2015151775A1 WO 2015151775 A1 WO2015151775 A1 WO 2015151775A1 JP 2015057714 W JP2015057714 W JP 2015057714W WO 2015151775 A1 WO2015151775 A1 WO 2015151775A1
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group
layer
photoelectrode
water
water splitting
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Japanese (ja)
Inventor
知里 片山
一成 堂免
苗 鐘
隆史 久富
耕 嶺岸
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Fujifilm Corp
University of Tokyo NUC
Japan Technological Research Association of Artificial Photosynthetic Chemical Process
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Fujifilm Corp
University of Tokyo NUC
Japan Technological Research Association of Artificial Photosynthetic Chemical Process
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    • C—CHEMISTRY; METALLURGY
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    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
    • C01B3/04—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of inorganic compounds, e.g. ammonia
    • C01B3/042—Decomposition 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
    • C25B1/01—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
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    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/847—Vanadium, niobium or tantalum or polonium
    • B01J23/8472—Vanadium
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/24—Nitrogen compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
    • B01J35/39—Photocatalytic properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0215—Coating
    • B01J37/0217—Pretreatment of the substrate before coating
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0215—Coating
    • B01J37/0225—Coating of metal substrates
    • B01J37/0226—Oxidation of the substrate, e.g. anodisation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0215—Coating
    • B01J37/0228—Coating in several steps
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
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    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/08—Heat treatment
    • B01J37/10—Heat treatment in the presence of water, e.g. steam
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
    • B01J37/341—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation
    • B01J37/347—Ionic or cathodic spraying; Electric discharge
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
    • B01J37/348—Electrochemical processes, e.g. electrochemical deposition or anodisation
    • 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

Definitions

  • the present invention relates to a water splitting photoelectrode, and more particularly to a water splitting photoelectrode provided with a coating layer formed using an atomic layer deposition method (ALD method).
  • ALD method atomic layer deposition method
  • the present invention also relates to a water splitting apparatus having the water splitting photoelectrode.
  • Patent Document 1 From the viewpoint of reducing carbon dioxide emissions and cleaning energy, attention has been focused on technologies for producing hydrogen and oxygen by using solar energy to decompose water using a photocatalyst. There have been many studies on water-splitting reactions using photocatalysts. For example, there is a study to effectively use visible light (for example, Patent Document 1).
  • Patent Document 1 Ta 3 N 5 or the like is exemplified as a photocatalyst.
  • an object of the present invention is to provide a water splitting photoelectrode exhibiting a good onset potential. Another object of the present invention is to provide a water splitting apparatus having the water splitting photoelectrode.
  • the present inventors have found that the above problem can be solved by using a coating layer containing a metal oxide semiconductor formed using an atomic layer deposition method. I found it. That is, the present inventors have found that the above problem can be solved by the following configuration.
  • a support which is disposed on the support, absorbs visible light, and includes groups 4A, 5A, 6A, 1B, 2B, A photocatalyst layer comprising a photosemiconductor having at least one metal element selected from the group consisting of a group 3B element and a group 4B element; and a photocatalyst layer disposed on the photocatalyst layer and formed using an atomic layer deposition method. And a coating layer containing a metal oxide semiconductor, wherein the coating layer has a thickness of 3 to 40 nm.
  • a water splitting apparatus comprising the water splitting photoelectrode according to any one of (1) to (5).
  • the photoelectrode for water splitting which shows a favorable onset potential can be provided.
  • the water splitting apparatus which has the said photoelectrode for water splitting can also be provided.
  • a numerical range represented by using “to” means a range including numerical values described before and after “to” as a lower limit value and an upper limit value.
  • the coating layer obtained by the atomic layer deposition method is uniformly deposited on the photocatalyst layer and easily interacts with the photocatalyst layer (for example, charge separation).
  • “onset potential is good” means that when the water splitting photoelectrode is an anode electrode, the value of the onset potential is on the lower side, and the water splitting photoelectrode is a cathode. In the case of an electrode, it is intended that the value of the onset potential is on the noble side.
  • the water-decomposing photoelectrode of the present invention exhibits excellent onset potential, high photocurrent density, and excellent change in photocurrent density even during continuous light irradiation. Shows durability.
  • FIG. 1 is a schematic cross-sectional view of one embodiment of a water splitting photoelectrode.
  • the water splitting photoelectrode 10 includes a support 12, a photocatalyst layer 14, and a coating layer 16.
  • a support 12 a support 12
  • a photocatalyst layer 14 a photocatalyst layer 14
  • a coating layer 16 a coating layer 16.
  • the support is a base material that supports the photocatalyst layer and the coating layer, and a known support can be used.
  • the support is formed of a metal, a non-metal such as carbon (graphite), or a conductive material such as a conductive oxide. It is preferable to use a supported support. Especially, since it has favorable workability, it is particularly preferable to use a metal support.
  • a simple substance of an atom exhibiting good electrical conductivity or an alloy can be used. Specific examples of the atomic simple substance include Au, Ti, Zr, Nb, and Ta. Specific examples of the alloy include carbon steel and titanium alloy.
  • the alloy is not limited to the exemplified materials as long as it is electrochemically stable.
  • the shape of the support is not particularly limited, and may be, for example, a punching metal shape, a mesh shape, a lattice shape, or a porous body having penetrating pores.
  • the support may be a laminate in which a plurality of layers are laminated (for example, a laminate of a glass substrate and a metal layer).
  • a photocatalyst layer is a layer arrange
  • the optical semiconductor constituting the photocatalyst layer is a material (semiconductor) that absorbs visible light, and includes Group 4A element (Group 4 element), Group 5A element (Group 5 element), and Group 6A in the periodic table. Element (Group 6 element), Group 1B element (Group 11 element), Group 2B element (Group 12 element), Group 3B element (Group 13 element), and Group 4B element (Group 14)
  • the onset potential is better, the photocurrent density is higher, or the durability by continuous irradiation is more excellent (hereinafter also referred to simply as “the effect of the present invention is more excellent”).
  • Is preferably Ti, V, Nb, Ta, W, Mo, Zr, Ga, In, Zn, Cu, Ag, Cd, Cr, or Sn, and more preferably Ti, V, Nb, Ta, or W.
  • the optical semiconductor include oxides, nitrides, oxynitrides, (oxy) chalcogenides, and the like containing the above metal elements.
  • the absorption of visible light is intended to absorb light in the visible light region (450 to 800 nm).
  • the photocatalyst layer usually contains a photo semiconductor as a main component.
  • the main component means that the photo semiconductor is 80% by mass or more with respect to the total mass of the photocatalyst layer, and preferably 90% by mass or more.
  • the upper limit is not particularly limited, but is 100% by mass.
  • the optical semiconductor may be a p-type semiconductor or an n-type semiconductor, but a suitable combination is preferably selected depending on the relationship with a metal oxide semiconductor contained in a coating layer described later.
  • a suitable combination is a combination A in which the optical semiconductor is a p-type semiconductor and the metal oxide semiconductor is an n-type semiconductor, or a combination in which the optical semiconductor is an n-type semiconductor and the metal oxide semiconductor is a p-type semiconductor. B is mentioned. With these combinations, charge separation is likely to occur between the photocatalyst layer and the coating layer, and as a result, the effects of the present invention are more excellent. Especially, the said combination B is preferable at the point which the effect of this invention is more excellent.
  • optical semiconductor examples include, for example, Bi 2 WO 6 , BiVO 4 , BiYWO 6 , In 2 O 3 (ZnO) 3 , InTaO 4 , InTaO 4 : Ni (“optical semiconductor: M” is M in the optical semiconductor.
  • optical semiconductor: M is M in the optical semiconductor.
  • M2 is co-doped, and so on.
  • TiO 2 Ni / Nb, TiO 2 : Cr / Sb, TiO 2 : Ni / Sb, TiO 2 : Sb / Cu, TiO 2 : Rh / Sb , TiO 2: Rh / Ta, TiO 2: Rh / Nb, SrTiO 3: Ni / Ta, SrTiO 3: Ni / Nb, SrTiO 3: Cr, SrTiO 3: Cr / Sb, SrTiO 3: r / Ta, SrTiO 3: Cr / Nb, SrTiO 3: Cr / W, SrTiO 3: Mn, SrTiO 3: Ru, SrTiO 3: Rh, SrTiO 3: Rh / Sb, SrTiO 3: Ir, CaTiO 3: Rh, La 2 Ti 2 O 7 : Cr, La 2 Ti 2 O 7 : Cr / S
  • the shape of the optical semiconductor contained in the photocatalyst layer is not particularly limited, and examples thereof include a columnar shape and a particle shape.
  • the particle size of the primary particles is not particularly limited, but is usually preferably 0.01 ⁇ m or more, more preferably 0.1 ⁇ m or more, and usually 50 ⁇ m or less. More preferably, it is 10 ⁇ m or less.
  • the above particle diameter is an average particle diameter.
  • the particle diameters (diameters) of 100 arbitrary optical semiconductors observed with a TEM (Transmission Electron Microscope) or SEM (Scanning Electron Microscope) were measured, and they were arithmetically averaged. Is.
  • the major axis is measured.
  • the optical semiconductor is columnar, it is preferably a columnar optical semiconductor extending along the normal direction of the support surface.
  • the diameter of the columnar optical semiconductor is not particularly limited, but is usually preferably 25 nm or more, more preferably 50 nm or more, and usually 20 ⁇ m or less, more preferably 10 ⁇ m or less.
  • the above-mentioned diameter is an average diameter, and any 100 columnar shapes observed with TEM (device name: Hitachi High-Technologies Corporation H-8100) or SEM (device name: Hitachi High-Technologies Corporation SU-8020 type SEM) The diameter of the optical semiconductor is measured, and the average of them is obtained.
  • the co-catalyst may be supported on the optical semiconductor as necessary.
  • Co-catalysts include Group 2-14 metals, intermetallic compounds of these metals, alloys, or oxides, composite oxides, nitrides, oxynitrides, sulfides, oxysulfides, or these It is preferable to use any one of the following mixtures.
  • NiO itself contained in a coating layer to be described later may simultaneously serve as a promoter.
  • the “intermetallic compound” is a compound formed from two or more kinds of metal elements, and the atomic ratio of the components constituting the intermetallic compound is not necessarily a stoichiometric ratio, but has a wide composition range. Say.
  • These oxides, composite oxides, nitrides, oxynitrides, sulfides, oxysulfides are metals in Group 2-14, intermetallic compounds of these metals, or oxides and composites of alloys. Oxides, nitrides, oxynitrides, sulfides, oxysulfides. “A mixture thereof” refers to a mixture of two or more of the compounds exemplified above.
  • the promoter is preferably a metal of Ti, Mn, Fe, Co, Ni, Cu, Ru, Rh, Pd, Ag, In, Ta, W, Ir, or Pt, or an oxide or composite oxide thereof.
  • Mn, Co, Ni, Ru , Rh, Ir metal an oxide thereof or composite oxides, more preferably, Ir, MnO, MnO 2, Mn 2 O 3, Mn 3 O 4 , CoO, Co 3 O 4 , NiCo 2 O 4 , RuO 2 , Rh 2 O 3 , IrO 2 .
  • the amount of the promoter supported is not particularly limited, but is preferably 0.01 to 10% by mass, more preferably 0.01 to 7% by mass, and more preferably 0.05 to 5% by mass based on the optical semiconductor (100% by mass). % Is more preferable.
  • the thickness of the photocatalyst layer is not particularly limited, but is preferably from 0.01 to 3.0 ⁇ m, more preferably from 0.1 to 2.0 ⁇ m, from the viewpoint of more excellent water splitting efficiency of the water splitting photoelectrode.
  • the method for forming the photocatalyst layer is not particularly limited, and a known method (for example, a method of depositing a particulate photo semiconductor on a support) can be employed. More specifically, the transfer method described in Chem. Sci., 2013, 4, 1120-1124, Adv. Mater. , 2013, 25, 125-131. Note that another layer (for example, an adhesive layer) may be included between the support and the photocatalyst layer as necessary.
  • the coating layer is a layer disposed on the photocatalyst layer and formed using an atomic layer deposition method.
  • the atomic layer deposition method is suitable for forming a very thin film in order to enable film formation for each atomic layer. More specifically, in general, a method is used in which two or more kinds of gaseous raw materials are alternately supplied to the reaction chamber to cause a chemical reaction on the film formation surface to form a film. Can be formed with high accuracy.
  • the atomic layer deposition method can be performed using a known apparatus. In addition, as the raw material to be used, an optimum material is selected according to the composition of the coating layer.
  • an atomic layer made of nickel oxide water molecules are supplied onto the photocatalyst layer, then a nickel precursor is further supplied, and then excess molecules are desorbed from nickel oxide (NiO).
  • NiO nickel oxide
  • An atomic layer is formed. However, it may be partially changed to HO—Ni ⁇ O due to a reaction with water vapor or moisture in the atmosphere. More specifically, in the above case, water vapor is introduced onto the photocatalyst layer, exhausted once (first exhaust), then nickel precursor is introduced, exhausted once (second exhaust), and then nitrogen gas is introduced.
  • ALD method atomic layer deposition method
  • the above steam pulse is preferably 1 to 5 seconds
  • the first exhaust is preferably 3 to 12 seconds
  • the nickel precursor pulse is preferably 3 to 12 seconds
  • the second exhaust is preferably 2 to 10 seconds
  • nitrogen filling Is preferably 1 to 5 seconds.
  • the time of the said pulse intends the time of the process which supplies water vapor
  • the nitrogen filling is preferably performed at a pressure of 0.8 to 1.2 Torr.
  • the thickness of the coating layer is 3 to 40 nm, and 3 to 18 nm is more preferable because the effect of the present invention is more excellent.
  • the said thickness is an average thickness, measures the thickness of arbitrary 5 points
  • the atomic layer deposition method is preferably performed under the condition of 100 to 400 ° C., more preferably 220 to 310 ° C., in that the effect of the present invention is more excellent.
  • the temperature control methods there is a method of controlling the temperature of the stage on which the support is placed, and it is preferable to adjust the temperature of the stage to the above temperature range as one of preferred embodiments. .
  • the coating layer includes a metal oxide semiconductor.
  • a p-type semiconductor or an n-type semiconductor can be used as the metal oxide semiconductor.
  • the type of the metal element contained in the metal oxide semiconductor is not particularly limited, but the rhodium element, chromium element, cobalt element, copper element, aluminum element, nickel element, iron element, silicon element are more effective in the present invention. At least one selected from the group consisting of lithium element, magnesium element, and calcium element is preferable, and nickel element is more preferable.
  • Specific examples of the metal oxide semiconductor include Rh 2 O 3 , Cr 2 O 3 , CoOx, NiO, CuCo 2 O 4 , MgFe 2 O 4 , CaFe 2 O 4 , and CuAl 2 O 4 .
  • NiO nickel oxide
  • a precursor metal oxide semiconductor precursor
  • a compound for example, a complex
  • the coating layer usually contains a metal oxide semiconductor as a main component.
  • the main component means that the metal oxide semiconductor is 60% by mass or more with respect to the total mass of the coating layer, and is preferably 85% by mass or more.
  • the upper limit is not particularly limited, but is 100% by mass.
  • the pretreatment which carries out UV (ultraviolet) ozone treatment on the surface of a photocatalyst layer.
  • the conditions for the UV ozone treatment are not particularly limited, but the flow rate of supplied oxygen is preferably 1 to 10 ml / min.
  • the treatment time is preferably 3 to 20 minutes.
  • the wavelength range of the irradiated UV is preferably 185 to 254 nm, the output is preferably 20 to 45 W, and the irradiation intensity is preferably 2000 to 3500 ⁇ W / cm 2 .
  • the annealing conditions are not particularly limited, but the heating temperature is preferably 200 to 450 ° C., more preferably 250 to 450 ° C., the heating time is preferably 0.25 to 1.5 hours, and more preferably 0.5 to 1 hour. preferable.
  • the temperature control methods there is a method of controlling the temperature of the stage on which the support is placed, and it is preferable to adjust the temperature of the stage to the above temperature range as one of preferred embodiments. .
  • the annealing method is not particularly limited, and a known oven or the like can be used.
  • the atomic layer deposition method when the atomic layer deposition method is performed in a chamber under a predetermined high temperature condition, after the atomic layer deposition method, the chamber is left to stand at room temperature in a low vacuum state in the presence of nitrogen, thereby annealing treatment. May be implemented.
  • the water splitting photoelectrode including the above-described support, photocatalyst layer, and coating layer produces the above-described excellent effects.
  • the water splitting photoelectrode can be suitably used as a so-called anode electrode.
  • sunlight etc. are mentioned as irradiated light.
  • the water-splitting apparatus provided with the said water-decomposition photoelectrode shows the outstanding characteristic, structures (for example, counter electrodes etc.) other than a water-decomposition photoelectrode can use a well-known structure.
  • a porous anodized aluminum mask was prepared. Anodization was sufficiently performed until the anodized aluminum mask reached the Ta substrate. In the formed anodized aluminum mask, nanochannels (through holes) penetrating from the exposed surface of the film to the surface on the Ta substrate side were formed. Next, the Ta substrate on which the anodized aluminum mask is arranged is immersed in a 0.5M H 3 BO 3 aqueous solution (60 ° C., 90 seconds), and then anodized on a magnetic stirrer at room temperature. did. The applied voltage was increased stepwise from 0 V to 650 V at 0.1 V / s and then held at 650 V for 1 hour.
  • Ta 3 N 5 was a columnar structure (nanorod) extending in the normal direction to the surface of the Ta substrate.
  • the obtained solution was sealed in a 100 ml Teflon (registered trademark) inner cylinder stainless steel autoclave and subjected to microwave hydrothermal reaction at 200 ° C. for 60 minutes to produce BiVO 4 .
  • a porcelain crucible suspension of BiVO 4 (solvent: H 2 O) was prepared, and the aqueous solution of cobalt nitrate at a mass ratio of Co / BiVO 4 ⁇ (Co / BiVO 4) ⁇ 100 ⁇ 0.5 It added so that it might become a mass%.
  • the magnetic crucible was heated with water vapor rising from a beaker containing boiling water and stirred with a glass rod.
  • the obtained powder was heat-treated at 400 ° C.
  • BiVO 4 carrying 0.5% by mass of a cobalt oxide promoter.
  • the obtained BiVO 4 supporting cobalt oxide was suspended in a low boiling point organic solvent (solvent: isopropyl alcohol) and applied on a support (FL (float) glass), and then a niobium layer (100 nm) Subsequently, a titanium conductive layer (2-3 ⁇ m) is sputtered, and a titanium transfer layer, an adhesive layer, a photocatalyst layer, and a particle transfer method (described in Chem. Sci., 2013, 4, 1120-1124) However, the laminated body laminated
  • the obtained powder was heat-treated at 400 ° C. to 500 ° C. for 1 hour under an ammonia stream (200 sccm), and further heat-treated at 200 ° C. for 1 hour under an oxygen atmosphere.
  • Supported LaTiO 2 N was produced.
  • the obtained LaTiO 2 N loaded with cobalt oxide was suspended in a low boiling point organic solvent (solvent: isopropyl alcohol) and applied on a support (FL glass (float glass)), and then a tantalum layer, Subsequently, the titanium conductive layer is sputtered, and the titanium conductive layer, the adhesive layer, and the photocatalyst layer are laminated in this order by a particle transfer method (described in Chem. Sci., 2013, 4, 1120-1124). A laminate was prepared.
  • Example 1 (Formation of coating layer by atomic deposition method (ALD treatment))
  • the Ta substrate provided with the Ta 3 N 5 layer manufactured in Synthesis Example 1 was placed on the stage, and the temperature was adjusted so that the temperature of the stage was 250 ° C.
  • Water is adsorbed on the surface of the Ta 3 N 5 layer that has been subjected to the UV ozone treatment, purge (first exhaust) is performed, then Ni precursor is adsorbed, and further purge (second exhaust) is performed to remove Ni.
  • the process of laminating the NiO layer was repeated 250 times by desorbing the ligand and water atom-derived hydrogen atoms in the precursor and filling with nitrogen (300 sccm).
  • the source gas is supplied in pulses, and the breakdown of one cycle consists of the water vapor pulse for 3 seconds, the purge (first exhaust) for 8 seconds, the Ni precursor pulse for 3 seconds, and the purge (second exhaust) for 8 seconds. Nitrogen filling was performed for 3 seconds.
  • the equipment used was Beneq TFS 200.
  • the Ni precursor (nickel precursor) is a solid of bis (2,2,6,6-tetramethylheptane-3,5-dionato) nickel (II) (Ni (thd) 2) (Wako Pure Chemical). (Carbon content 62.2% by mass, hydrogen content 9.0% by mass, Ni content about 14% by mass) was used.
  • the thickness (average thickness) of the obtained NiO layer was 7.5 nm.
  • Example 1 except that the type of the photocatalyst layer used (see Synthesis Examples 1 to 3), the temperature of the annealing process, or the number of cycles in the ALD process was changed and the thickness of the NiO layer was changed as shown in Table 1.
  • a water-decomposing photoelectrode was produced according to the same procedure as described above. For Examples 11 to 13, the following (UV ozone pretreatment) was performed before the ALD treatment. In the water splitting photoelectrodes obtained in Examples 1 to 13, the optical semiconductor (Ta 3 N 5 , LaTiO 2 N, BiVO 4) is an n-type semiconductor, and NiO functions as a p-type semiconductor. .
  • UV ozone pretreatment In order to increase the hydrophilicity of the surface of the photocatalyst layer obtained in Synthesis Example 2, UV ozone treatment was performed. Oxygen gas was used, the treatment time was 15 minutes, and the oxygen flow rate was 5 ml / min. The UV light output was 270 W, the wavelength was 185 nm-254 nm, and the irradiation intensity was 28000 ⁇ W / cm 2 . Moreover, the chamber volume which performed UV ozone treatment was 6L.
  • Comparative Examples 1 to 9 The water splitting of Comparative Examples 1 to 4 and 6 was carried out according to the same procedure as in Example 1 except that the type of photocatalyst layer used was changed as shown in Table 1 and the ALD process was not performed. A photoelectrode was manufactured.
  • the mass ratio ⁇ (Co / LaTiO 2 N) ⁇ 100 ⁇ is 2.5 mass%
  • the mass ratio ⁇ (Co / LaTiO 2 N) ⁇ 100 ⁇ is 5.0.
  • the mass ratio ⁇ (Co / LaTiO 2 N) ⁇ 100 ⁇ in Comparative Example 4 was 3.0 mass%.
  • Example 1 was changed except that the thickness of the NiO layer was changed as shown in Table 1 by changing the type of photocatalyst layer to be used, the temperature of annealing treatment, or the number of cycles in ALD treatment.
  • a water-decomposing photoelectrode was produced according to the same procedure as described above.
  • the thickness of the NiO layer was 1.5 nm.
  • the type of photocatalyst layer to be used and the supported amount of the cocatalyst were changed as shown in Table 1 to be described later.
  • the current value was set to 77.5 A using a vacuum evaporation apparatus, and Ni was Except for vapor deposition and deposition of NiO to a thickness of 2 nm, water splitting photoelectrodes of Comparative Examples 7 to 9 were produced according to the same procedure as in Example 1 above. Note that VPC-260F manufactured by ULVAC-RIKO was used as the vacuum deposition apparatus.
  • the photocurrent density of the produced water splitting photoelectrode was evaluated by measuring the current-potential in a three-electrode system using a potentiostat. A separable flask with a flat window was used for the electrochemical cell, an Ag / AgCl electrode for the reference electrode, and a Pt wire for the counter electrode.
  • the water splitting photoelectrode of the present invention exhibits excellent characteristics.
  • the water splitting photoelectrode of the present invention shows a lower onset potential.
  • the same tendency was confirmed from the comparison between Examples 4 to 10 and Comparative Examples 2 to 5 and the comparison between Examples 11 to 13 and Comparative Example 6.
  • the evaluation of “durability” was not measured.
  • Comparative Examples 1 to 9 in which the ALD process for forming a predetermined coating layer thickness was not performed, the desired effect was not obtained.
  • Example 14 Except that the amount of CoOx cocatalyst supported was 0.1% by mass, the generated water decomposition photoelectrode was used to quantitate the generated gas qualities and the generated amount in the same manner as in Example 12. It was.
  • the applied voltage was 1.0 V RHE .
  • the photocurrent density was evaluated by current-time measurement in a three-electrode system using a potentiostat (Hokuto Denko Co., Ltd., Automatic Polarization System HSV-110). A separable flask corresponding to upper irradiation was used for an electrochemical cell, an Ag / AgCl electrode was used as a reference electrode, and a CrOx / Pt wire was used as a counter electrode.
  • a solar simulator AM1.5G
  • a micro GC system Inficon Co., Ltd. 3000 Micro GC gas analyzer
  • the reaction was carried out for 12 hours, and it was confirmed that hydrogen and oxygen were generated stoichiometrically. It was also confirmed that the Faraday efficiency was almost 100%. The results are shown in Table 2.

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Abstract

L'invention concerne une photoélectrode destinée à être utilisée dans la décomposition d'eau, qui présente un bon potentiel de départ. La photoélectrode destinée à être utilisée dans la décomposition de l'eau selon la présente invention est équipée : d'un corps de support ; d'une couche de photocatalyseur qui est disposée sur le corps de support, peut absorber la lumière visible, et comprend un semi-conducteur optique ayant au moins un élément métallique choisi dans le groupe constitué d'éléments du groupe 4A, d'éléments du groupe 5A, d'éléments du groupe 6A, d'éléments du groupe 1B, d'éléments du groupe 2B, d'éléments du groupe 3B et d'éléments du groupe 4B du tableau périodique des éléments ; et d'une couche de revêtement qui est disposée sur la couche de photocatalyseur, est formée au moyen d'un procédé de dépôt de couche atomique, et contient un semi-conducteur à oxyde métallique. Dans la photoélectrode, la couche de revêtement a une épaisseur de 3 à 40 nm.
PCT/JP2015/057714 2014-03-31 2015-03-16 Photoélectrode à utiliser dans la décomposition d'eau, et dispositif de décomposition d'eau Ceased WO2015151775A1 (fr)

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JP2017043816A (ja) * 2015-08-28 2017-03-02 富士フイルム株式会社 水分解用光触媒電極およびこれの製造方法
CN110586068A (zh) * 2019-09-06 2019-12-20 西安建筑科技大学 一种镱离子掺杂改性BiVO4光电催化电极的制备方法、产品及其应用
CN113795611A (zh) * 2019-05-05 2021-12-14 多伦多大学管理委员会 在电解池中碳酸盐转化为合成气或c2+产物
WO2022235721A1 (fr) * 2021-05-06 2022-11-10 Global Advanced Metals Usa, Inc. Nitrure de tantale dopé avec un ou plusieurs métaux, catalyseur, procédés pour la décomposition de l'eau à l'aide du catalyseur, et procédés pour fabriquer celui-ci
US20230191371A1 (en) * 2020-06-24 2023-06-22 Guangdong Brunp Recycling Technology Co., Ltd. Photocatalyst and application thereof in environmentally friendly photocatalytic treatment of power battery

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JP6708927B2 (ja) 2016-04-28 2020-06-10 富士通株式会社 光化学電極
JP2020054931A (ja) * 2017-01-27 2020-04-09 国立研究開発法人科学技術振興機構 構造物及びその製造方法

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JP2017043816A (ja) * 2015-08-28 2017-03-02 富士フイルム株式会社 水分解用光触媒電極およびこれの製造方法
CN113795611A (zh) * 2019-05-05 2021-12-14 多伦多大学管理委员会 在电解池中碳酸盐转化为合成气或c2+产物
CN110586068A (zh) * 2019-09-06 2019-12-20 西安建筑科技大学 一种镱离子掺杂改性BiVO4光电催化电极的制备方法、产品及其应用
CN110586068B (zh) * 2019-09-06 2022-03-25 西安建筑科技大学 一种镱离子掺杂改性BiVO4光电催化电极的制备方法、产品及其应用
US20230191371A1 (en) * 2020-06-24 2023-06-22 Guangdong Brunp Recycling Technology Co., Ltd. Photocatalyst and application thereof in environmentally friendly photocatalytic treatment of power battery
US11826729B2 (en) * 2020-06-24 2023-11-28 Guangdong Brunp Recycling Technology Co., Ltd. Photocatalyst and application thereof in environmentally friendly photocatalytic treatment of power battery
WO2022235721A1 (fr) * 2021-05-06 2022-11-10 Global Advanced Metals Usa, Inc. Nitrure de tantale dopé avec un ou plusieurs métaux, catalyseur, procédés pour la décomposition de l'eau à l'aide du catalyseur, et procédés pour fabriquer celui-ci

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