WO2022024747A1 - Dispositif de séparation d'eau et procédé de production de gaz - Google Patents

Dispositif de séparation d'eau et procédé de production de gaz Download PDF

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WO2022024747A1
WO2022024747A1 PCT/JP2021/026291 JP2021026291W WO2022024747A1 WO 2022024747 A1 WO2022024747 A1 WO 2022024747A1 JP 2021026291 W JP2021026291 W JP 2021026291W WO 2022024747 A1 WO2022024747 A1 WO 2022024747A1
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photocatalyst
aqueous solution
surfactant
water
gas
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PCT/JP2021/026291
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English (en)
Japanese (ja)
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佳紀 前原
大成 西見
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富士フイルム株式会社
人工光合成化学プロセス技術研究組合
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Publication of WO2022024747A1 publication Critical patent/WO2022024747A1/fr

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    • 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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/66—Silver or gold
    • B01J23/68—Silver or gold with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • 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
    • 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
    • C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
    • C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
    • 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
    • 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 device and a method for producing a gas.
  • Patent Document 1 a base material with a photocatalyst having a base material and a photocatalyst fixed on the base material is placed in water, and the base material with a photocatalyst is irradiated with light to decompose water.
  • Methods for producing at least one of hydrogen and oxygen are disclosed.
  • an object of the present invention is to provide a water splitting device having an excellent initial amount of gas generated and a method for producing gas.
  • the present inventors fixed the container containing the aqueous solution containing the surfactant on the photocatalytic substrate or the inner wall surface of the container immersed in the aqueous solution.
  • water splitting was carried out using a water splitting device having the photocatalyst, it was found that the initial amount of gas generated was excellent.
  • a container containing an aqueous solution containing a surfactant It has a base material and a photocatalyst-attached base material having a photocatalyst fixed on the base material, or a photocatalyst fixed on the inner wall surface of the container, which is immersed in the aqueous solution.
  • a water decomposition device that generates gas from the photocatalyst by irradiating the photocatalyst with light.
  • the photocatalyst comprises at least one photocatalytic compound selected from the group consisting of oxides, oxynitrides, nitrides and chalcogenide compounds.
  • the photocatalyst compounds are Sr, Na, Mg, Al, Si, Ca, Ti, V, Fe, Cu, Zn, Ga, Y, Zr, Nb, Ag, In, Sn, Ba, La, Ta, W and Bi.
  • the water splitting apparatus according to any one of [1] to [5], which comprises at least one element selected from the group consisting of.
  • the embodiment of the water splitting apparatus of this invention is schematically an end view. It is a schematic diagram which shows the gas generation amount measurement system used in the Example column.
  • the numerical range represented by using "-" means a range including the numerical values before and after "-" as the lower limit value and the upper limit value.
  • the visible light is light having a wavelength visible to the human eye among electromagnetic waves, and specifically, light in a wavelength range of 380 to 780 nm.
  • the water splitting apparatus of the present invention is a container containing an aqueous solution containing a surfactant, a base material with a photocatalyst having a base material and a photocatalyst fixed on the base material, or a base material having a photocatalyst, which is immersed in the aqueous solution.
  • the water splitting apparatus of the present invention is excellent in the initial amount of gas generated. The details of this reason have not been clarified, but it is presumed that it is due to the following reasons.
  • Examples of the water splitting device include a photocatalyst-equipped substrate in which a photocatalyst in which a hydrogen generation reaction and an oxygen generation reaction occur on the same particle is immobilized on the substrate, and a photocatalyst in which a hydrogen generation reaction and an oxygen generation reaction occur on the same particle.
  • the photocatalyst immobilized on the inner wall surface of the container, the photocatalyst-equipped substrate in which the photocatalyst compound for hydrogen generation and the photocatalyst compound for oxygen generation are immobilized on the substrate, and the photocatalyst compound for hydrogen generation and the photocatalyst compound for oxygen generation are inside.
  • An embodiment having a photocatalyst immobilized on a wall surface can be mentioned.
  • FIG. 1 is an end view schematically showing a water splitting device 1 which is an example of the water splitting device of the present invention.
  • the water splitting device 1 has a container 10 filled with an aqueous solution S containing a surfactant, and a photocatalytic substrate 20 arranged in the container 10.
  • the photocatalyst-attached base material 20 has a base material 22 and a photocatalyst 24 fixed on the base material 22.
  • the base material 20 with a photocatalyst 20 is arranged in the container 20 at a position where the photocatalyst 24 can receive light L.
  • the water decomposition device 1 is a device that generates a gas from the surface of the photocatalyst 24 by irradiation with light L. Specifically, irradiation of the photocatalyst 24 with light L causes decomposition of water on the surface of the photocatalyst 24, and at least one of oxygen and hydrogen is generated.
  • the light L to be irradiated visible light such as sunlight, ultraviolet light, infrared light and the like can be used, and among them, sunlight whose amount is inexhaustible is preferable.
  • the container 10 is a container that contains the aqueous solution S and is used for installing the base material 20 with a photocatalyst.
  • the shape of the container 10 is not particularly limited as long as it can accommodate the aqueous solution S and the base material 20 with a photocatalyst can be installed.
  • Specific examples of the material constituting the container 10 are preferably a material having excellent corrosion resistance, and examples thereof include polyacrylate, polymethacrylate, polycarbonate, polypropylene, polyethylene, polystyrene, polyethylene terephthalate, polyethylene naphthalate, glass, and metal. ..
  • the aqueous solution S is an aqueous solution in which a surfactant is dissolved in water, and is contained in a container 10.
  • the aqueous solution S is a raw material used for water decomposition.
  • Specific examples of the surfactant include ionic surfactants such as cationic surfactants, anionic surfactants and amphoteric surfactants, and nonionic surfactants.
  • the cationic surfactant include aliphatic amine salts, aliphatic quaternary ammonium salts, aromatic quaternary ammonium salts, benzalkonium chloride salt, benzethonium chloride, pyridinium salt, imidazolinium salt and the like. ..
  • Specific examples of the anionic surfactant include carboxylates, sulfonates (eg, alkyl sulfonates, alkylbenzene sulfonates), sulfate ester salts, phosphate ester salts and the like.
  • amphoteric tenside examples include carboxybetaine type, sulfobetaine type, aminocarboxylate, imidazolinium betaine, lecithin, alkylamine oxide and the like.
  • nonionic surfactants include polyoxyethylene higher alkyl ethers, polyoxyethylene higher alkylphenyl ethers, polyoxyethylene glycol higher fatty acid diesters, silicone-based surfactants, and fluorine-based surfactants. Agents and the like can be mentioned.
  • a fluorine-based surfactant in which a part of the carbon-hydrogen bond is replaced with a carbon-fluorine bond is preferably used because of its excellent stability.
  • the surfactant may be used alone or in combination of two or more.
  • the surfactant does not have a hydroxy group, an alkoxy group, and an ether bond that are easily oxidized on the photocatalyst surface because it can exist stably on the photocatalyst surface and the initial amount of gas generated is more excellent.
  • Aromatic rings eg, benzene, etc. that are easily oxidized by active oxygen species produced as reaction intermediates for water splitting, because the surfactant can exist stably during the water splitting reaction and the amount of initial gas generated is excellent. It is preferable not to have an aromatic hydrocarbon ring and an aromatic heterocycle such as imidazole, pyrazole and pyridine).
  • the surfactant contains a compound represented by the formula I because the elapsed value of the hydrogen generation rate is excellent (that is, the decrease in the hydrogen generation rate can be suppressed when the photocatalyst is irradiated with light for a long time). It is preferable, and it is particularly preferable that the compound is represented by the formula I.
  • R 1 is an alkyl group having 4 to 20 carbon atoms.
  • the alkyl group in R 1 may be linear, branched or cyclic.
  • the number of carbon atoms of the alkyl group in R1 is 4 to 20, and 6 to 18 is preferable, and 8 to 16 is particularly preferable, because the initial amount of gas generated and the elapsed value of the hydrogen generation rate are more excellent.
  • R 2 , R 3 and R 4 are independently alkyl groups. However, the carbon number of the alkyl group in R2 , R3 and R4 is less than or equal to the carbon number of the alkyl group of R1 .
  • the lower limit of the number of carbon atoms of the alkyl group in R 2 , R 3 and R 4 is 1.
  • the alkyl groups in R2 to R4 may be linear, branched or cyclic. R2 to R4 may be the same or different.
  • X ⁇ is a halide ion or a hydroxide ion.
  • a halide ion is preferable, and F ⁇ , Cl ⁇ , or Br ⁇ is more preferable because it is excellent in stability during a water splitting reaction.
  • the oxidation peak potential of the aqueous solution is 1 because the surfactant molecules are less likely to be oxidized on the surface of the photocatalyst and can exist stably, and the initial gas generation amount is excellent.
  • .0V vs. It is preferably RHE or higher, and 1.3 V vs. RHE or higher is more preferable, 1.6 V vs. RHE or higher is particularly preferable.
  • the upper limit of the oxidation peak potential of the aqueous solution is not particularly limited, but is 3.0 V vs. RHE or less is preferable.
  • RHE is an abbreviation for reversible hydrogen electrode.
  • the oxidation peak potential of the aqueous solution can be measured by the method described in the Example column described later. In addition, 0.5V vs. Since the oxidation peak potential appearing below RHE is the oxidation peak potential derived from the platinum electrode used for the measurement, 0.5 V vs. The oxidation peak potential that appears above RHE is the oxidation peak potential of the aqueous solution.
  • a surfactant having no aromatic ring is contained, and the oxidation peak potential of the aqueous solution is 1.0 V vs. Examples thereof include RHE and above.
  • an excellent water splitting device can be obtained due to the initial amount of gas generated.
  • One of the preferred embodiments of the aqueous solution in the present invention is a surfactant containing an aromatic ring, a hydroxy group, an alkoxy group, and an ether bond, and the oxidation peak potential of the aqueous solution is 1.0 V vs. Examples thereof include RHE and above.
  • a water splitting device having an excellent hydrogen generation rate can be obtained.
  • One of the preferred embodiments of the aqueous solution in the present invention includes an embodiment containing a surfactant satisfying the above formula I. As a result, a water splitting device having an excellent elapsed value of the hydrogen generation rate can be obtained.
  • the lower limit of the concentration of the surfactant in the aqueous solution is the critical micelle concentration peculiar to the surfactant because the decrease in surface tension makes it easier for bubbles to separate from the surface of the photocatalyst and the diffusion of the gas generated by water splitting is excellent. 0.25 times or more of (CMC) is preferable, 0.5 times or more of CMC is more preferable, and 1 time or more of CMC is particularly preferable.
  • the upper limit of the concentration of the surfactant in the aqueous solution is preferably 20 times or less of CMC, more preferably 10 times or less of CMC, and particularly preferably 5 times or less of CMC from the viewpoint of avoiding cloudiness of the aqueous solution.
  • the surface tension of water is measured by changing the concentration of the surfactant with a surface tension meter (manufactured by Kyowa Surfactant), and the surface tension and the surface are measured.
  • the concentration of the turning point in the tension plot (the lowest concentration at which the decrease in surface tension due to the increase in surfactant concentration is contained and the surface tension value becomes constant) is determined as the CMC value.
  • the CMC value can also be obtained by an electric conduction method, a dye method, a fluorescence method, or a viscosity method.
  • the CMC values of various surfactants described in the literature such as M. J. Rosen, J. T. Kunjappu, Surfactants and interfacial phenomena, 4th edition, John Wiley & Sons (2012) can also be referred to.
  • the photocatalyst-attached base material 20 has a base material 22 and a photocatalyst 24 immobilized on the base material 22.
  • the base material 20 with a photocatalyst is immersed in the aqueous solution 10 so that the photocatalyst 24 comes into contact with the aqueous solution 10.
  • the base material 22 is a member that supports the photocatalyst 24.
  • Specific examples of the material constituting the base material 22 include metals, organic compounds (for example, polyacrylate, polymethacrylate, polycarbonate, polypropylene, polyethylene, polystyrene, polyethylene terephthalate, polyethylene naphthalate), inorganic compounds (for example, SrTiO 3 and the like). Metal oxides, glass, ceramics).
  • the shape of the base material 22 is not particularly limited, and may be a flat plate shape, a punching metal shape, a mesh shape, a lattice shape, or a porous body having penetrating pores.
  • the thickness of the base material 22 is not particularly limited and can be appropriately selected depending on the size of the container 10.
  • the base material 22 has a single-layer structure, but the base material 22 may have a multi-layer structure.
  • the base material 22 may include a support layer and a conductive layer arranged on the support layer.
  • the material constituting the support layer include the material constituting the above-mentioned base material 22.
  • Materials constituting the conductive layer include metals (for example, Sn, Ti, Ta, Au), SrRuO 3 , ITO (indium tin oxide), and zinc oxide-based transparent conductive materials (Al: ZnO, In: ZnO, Ga: ZnO, etc.).
  • metal atom: metal oxide such as Al: ZnO
  • a part of the metal (Zn in the case of Al: ZnO) constituting the metal oxide is referred to as a metal atom (Al: ZnO). In the case, it means the one replaced with Al).
  • the photocatalyst 24 is fixed on the base material 22.
  • a gas specifically, at least one of oxygen and hydrogen
  • the photocatalyst 24 is arranged on a part of the base material 22, but may be arranged on the whole of the base material 22.
  • the photocatalyst 24 may exist in a form in which a plurality of photocatalyst particles are continuously present on the base material 22 (that is, a form constituting the photocatalyst layer), or a plurality of photocatalyst particles are present on the base material 22. It may exist in a form that exists discontinuously.
  • the thickness of the photocatalyst layer is preferably 0.1 to 1000 ⁇ m, and particularly preferably 1 to 100 ⁇ m.
  • the method for immobilizing the photocatalyst 24 on the substrate 22 is not particularly limited, and for example, the photocatalyst particles are dispersed in a solvent to form a suspension (slurry), and the suspension is applied onto the substrate.
  • a solvent examples include water, alcohols such as methanol and ethanol, ketones such as acetone, benzene, toluene and xylene.
  • the photocatalyst particles can be uniformly dispersed in the solvent by performing ultrasonic treatment.
  • the surfactant remaining in the photocatalyst layer reduces the reaction efficiency of the photocatalyst.
  • Suspensions that do not contain are preferred.
  • the method of applying the suspension on the substrate is not particularly limited, and for example, a drop casting method, a spray method, a dip method, a squeegee method, a doctor blade method, a spin coating method, a screen coating method, a roll coating method, and an inkjet method.
  • Known methods such as a method and a particle transfer method can be mentioned.
  • the temperature may be maintained at a temperature equal to or higher than the boiling point of the solvent.
  • Examples of the material constituting the photocatalyst 24 include at least one photocatalyst compound selected from the group consisting of oxides, oxynitrides, nitrides and chalcogenide compounds.
  • Photocatalytic compounds are from Sr, Na, Mg, Al, Si, Ca, Ti, V, Fe, Cu, Zn, Ga, Y, Zr, Nb, Ag, In, Sn, Ba, La, Ta, W and Bi. It is preferable to contain at least one element selected from the group.
  • One of the preferred embodiments of the photocatalyst 24 includes an embodiment containing both a photocatalyst compound for hydrogen generation and a photocatalyst compound for oxygen generation.
  • Specific examples of the photocatalyst compound for hydrogen generation include oxynitrides such as BaNbO 2 N, BaTaO 2 N, LaTIO 2 N, and TaON, nitrides such as Ta 3 N 5 , and Y 2 Ti 2 O 5 S 2 , and so on.
  • CZTS compound semiconductor such as Cu 2 ZnSnS 4 , Cr.
  • SrTIO 3 doped with at least one element selected from the group consisting of, Rh, Ta and Ir, and is not limited to the materials exemplified here, but is excellent in gas generation amount and durability.
  • CIGS compound semiconductors nitrides such as Ta 3 N 5 , and BaTaO 2 N, LaTIO 2 N and Acid nitrides such as TaON are preferred.
  • Specific examples of the photocatalytic compound for oxygen generation include oxides such as TIO 2 , Fe 2 O 3 , WO 3 , BiVO 4 , and Bi 2 WO 6 in addition to those exemplified for the photocatalytic compound for hydrogen generation.
  • Nitrides such as 5 and oxynitrides such as BaTaO 2 N, LaTIO 2 N and TaON are preferred.
  • One of the preferred embodiments of the photocatalyst 24 is a solid solution of GaN and ZnO, an oxynitride such as LaTIO 2 N and TaON, a nitride such as Ta 3 N 5 , Na 2 Ti 6 O 13 , SnNb 2 O 6 , BaTi.
  • KTaO 3 doped with at least one element selected from the group consisting of 4 O 9 , Na, Al, Cr, Ni, Rh, Sb and Ta hereinafter, also referred to as “specific element”
  • specific element include SrTiO 3 and at least one photocatalytic compound selected from the group consisting of TiO 2 doped with a specific element.
  • These photocatalytic compounds can generate both oxygen and hydrogen gases by water splitting with light irradiation. Of these, SrTiO 3 doped with a specific element is preferable from the viewpoint of excellent gas generation amount and durability.
  • the photocatalyst 24 may have a co-catalyst supported on its surface. If a co-catalyst is supported, the gas generation efficiency becomes better.
  • the method for supporting the co-catalyst is not particularly limited, and can be formed by, for example, a coating firing method, a photoelectric deposition method, a vacuum vapor deposition method, a sputtering method, an impregnation method, or the like.
  • Examples of the material constituting the co-catalyst include simple substances composed of Pt, Pd, Ni, Au, Ag, Ru, Cu, Co, Cr, Rh, Ir, Mn and the like, alloys obtained by combining them, and the like. Oxides can be mentioned.
  • the size of the co-catalyst is not particularly limited, and is preferably 0.5 nm to 1 ⁇ m and a height of about several nm.
  • the gas generated near the surface of the photocatalyst 24 can be recovered, for example, from a pipe (not shown) connected to the container 10. Further, a supply pipe (not shown), a pump, or the like for supplying the aqueous solution S may be connected to the container 10. Further, the water splitting device 1 may have a light source (xenon lamp or the like) (not shown) when sunlight is not used as the light L.
  • a light source xenon lamp or the like
  • the water splitting device of the present invention uses a photocatalyst fixed on the inner wall surface of the container instead of the base material with a photocatalyst. It may be a mode to have.
  • the photocatalyst may be immobilized at any position on the inner wall surface of the container as long as it is arranged at a position where it is immersed in the aqueous solution.
  • the method of immobilizing the photocatalyst on the inner wall surface of the container is not particularly limited, and examples thereof include the same method as the method of immobilizing the photocatalyst on the substrate.
  • the method for producing a gas of the present invention is a method for producing a gas using the above-mentioned water decomposition apparatus of the present invention, and by irradiating the photocatalyst of the above-mentioned water decomposition apparatus with light, gas is removed from the surface of the above-mentioned photocatalyst. generate.
  • Examples of the generated gas include hydrogen and oxygen.
  • the initial amount of gas generated is excellent.
  • Example 1 Manufacturing of base material with photocatalyst
  • powder of SrTiO 3 : Al which is a photocatalyst carrying RhCrO x , which is a hydrogen generation assisting catalyst, and hydrophilic silica particles are prepared.
  • Dispersed in pure water by ultrasonic treatment to obtain a suspension containing no surfactant.
  • This suspension was drop-cast on a glass plate, dried and immobilized, and cut into a 3 cm square square to obtain a photocatalytic substrate.
  • SrTiO 3 : Al means SrTiO 3 doped with Al.
  • Aqueous solution S1 is prepared by mixing and stirring dodecyltrimethylammonium bromide and pure water so that the concentration of dodecyltrimethylammonium bromide (cationic surfactant; see formula I-1 below) is as shown in Table 1.
  • the oxidation peak potential of the aqueous solution S1 was measured by electrochemical measurement using an electrochemical measurement system (Hokuto Denko, HZ-7000). Specifically, a reaction vessel made of borosilicate glass (diameter 6 cm, height 7 cm) is used, a platinum (Pt) wire is used as the working electrode and the counter electrode, and an Ag / AgCl electrode (Toyo Technica, TRE-10D-200) is used as the reference electrode. -INAGSE-20) was used.
  • Sodium dihydrogen phosphate (NaH 2 PO 4 , 0.05 mL / L) and disodium hydrogen phosphate (Na 2 HPO 4 , 0.05 mol / L) were added to the aqueous solution S1 as supporting electrolytes.
  • 0.1 L of the aqueous solution S1 to which the supporting electrolyte is added is poured into the reaction vessel, argon is allowed to flow in the reaction vessel for 10 minutes, and then electrochemical measurement is performed by a cyclic voltammetry method to determine the oxidation peak potential of the aqueous solution S1. I asked.
  • the sweep range is -0.1 V vs. RHE ⁇ 1.8V vs.
  • the number of bubbles detached from the surface of the photocatalyst within the observation range and time was measured, and the aqueous solution with respect to the number of bubbles detached in pure water.
  • the number of bubbles leaving was compared and evaluated. It can be said that the larger the number of bubbles released, the larger the initial amount of gas generated.
  • the evaluation criteria are as follows, and the results are shown in Table 1.
  • C The number of bubble separations is 1 times or less compared to pure water
  • the gas generation amount measuring system 500 includes a water decomposition device 100, a closed circulation reaction system 200 for an automatic double photocatalyst, a xenon lamp 300, and a gas chromatograph 400.
  • the water decomposition apparatus 100 has a reaction vessel 110 containing the aqueous solution S1 and a photocatalytic substrate 120 immersed in the aqueous solution S1.
  • the closed circulation reaction system 200 for an automatic double photocatalyst includes a pressure gauge 210, a circulation pump 220, a vacuum pump 230, and a pipe 240 connecting each member. Specifically, a base material 120 with a photocatalyst was placed on the bottom surface of the reaction vessel 110, and 0.1 L of the aqueous solution S1 was poured.
  • This reaction vessel 110 is connected to a closed circulation reaction system 200 for an automatic double photocatalyst, degassed under a reduced pressure of 10 Pa by a vacuum pump 230 for 1 hour, and then argon (Ar) is introduced to introduce 10 kPa. And said. Then, the base material 120 with a photocatalyst was irradiated with light L1 from the xenon lamp 300, and the amount of hydrogen and oxygen gas generated in the reaction vessel 110 was measured every hour by the gas chromatograph 400.
  • the "hydrogen generation rate” (hydrogen gas generation amount per hour) was calculated from the hydrogen gas generation amount 0 to 3 hours after the start of light irradiation, and used as the "initial value" of the hydrogen generation rate.
  • aqueous solution with respect to the "initial value" of an aqueous solution (hereinafter, also referred to as “reference aqueous solution”) having a concentration of octylphenol ethoxylate (Dow, TRITON (registered trademark) X-100, nonionic surfactant) of 1 mmol / L.
  • the "initial value” in S1 was compared and evaluated.
  • the evaluation criteria are as follows, and the results are shown in Table 1.
  • the initial value of the hydrogen generation rate is more than 4 times that of the reference aqueous solution
  • Examples 2 to 11 Various evaluations were performed in the same manner as in Example 1 except that the aqueous solutions S2 to S11 in Table 1 were used instead of the aqueous solution S1. The results are shown in Table 1. The outline of the surfactant contained in each aqueous solution is shown below. In addition, the critical micelle concentration (CMC) of each surfactant was calculated according to the above-mentioned method using a surface tension meter (manufactured by Kyowa Interface Science Co., Ltd.). Based on the CMC of each surfactant, the concentration of the surfactant in each aqueous solution is determined by how many times the concentration of the surfactant contained in each aqueous solution is compared with the CMC of the surfactant in Table 1. Shown in the column.
  • CMC critical micelle concentration
  • Water decomposition device 10 Container 20 Base material with photocatalyst 22 Base material 24 Photocatalyst S aqueous solution L Optical 100 Water decomposition device 110 Reaction container 120 Base material with photocatalyst 200 Closed circulation reaction system for automatic double photocatalyst 210 Pressure gauge 220 Circulation pump 230 Vacuum Pump 240 Piping 300 Xenon lamp 400 Gas chromatograph 500 Gas generation measurement system S1 Aqueous solution L1 Light

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Abstract

La présente invention aborde le problème de la fourniture d'un dispositif de séparation d'eau assurant une augmentation de la quantité initiale de gaz généré, et un procédé de production de gaz. Le dispositif de séparation d'eau selon la présente invention comprend : un récipient contenant une solution aqueuse contenant un tensioactif ; et un substrat revêtu de photocatalyseur immergé dans la solution aqueuse et ayant un substrat et un photocatalyseur fixé sur le substrat, ou un photocatalyseur fixé sur une surface de paroi interne du récipient. Le gaz est généré à partir du photocatalyseur par irradiation du photocatalyseur avec de la lumière.
PCT/JP2021/026291 2020-07-31 2021-07-13 Dispositif de séparation d'eau et procédé de production de gaz WO2022024747A1 (fr)

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4394293A (en) * 1979-09-08 1983-07-19 Engelhard Corporation Catalyst for the photolytic production of hydrogen from water
JP2006306667A (ja) * 2005-04-28 2006-11-09 Hamamatsu Photonics Kk 水素生成装置及び砕氷装置
JP2013237587A (ja) * 2012-05-15 2013-11-28 Toyota Motor Corp 光触媒を用いた水素生成装置
JP2017124393A (ja) * 2015-07-31 2017-07-20 Toto株式会社 光触媒材及びその製造方法

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4394293A (en) * 1979-09-08 1983-07-19 Engelhard Corporation Catalyst for the photolytic production of hydrogen from water
JP2006306667A (ja) * 2005-04-28 2006-11-09 Hamamatsu Photonics Kk 水素生成装置及び砕氷装置
JP2013237587A (ja) * 2012-05-15 2013-11-28 Toyota Motor Corp 光触媒を用いた水素生成装置
JP2017124393A (ja) * 2015-07-31 2017-07-20 Toto株式会社 光触媒材及びその製造方法

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