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WO2013115213A1 - Mésocristal d'oxyde de titane - Google Patents

Mésocristal d'oxyde de titane Download PDF

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Publication number
WO2013115213A1
WO2013115213A1 PCT/JP2013/051972 JP2013051972W WO2013115213A1 WO 2013115213 A1 WO2013115213 A1 WO 2013115213A1 JP 2013051972 W JP2013051972 W JP 2013051972W WO 2013115213 A1 WO2013115213 A1 WO 2013115213A1
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titanium oxide
tif
mesocrystal
crystal
oxide mesocrystal
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Japanese (ja)
Inventor
哲朗 真嶋
貴士 立川
ジンフン ビエン
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University of Osaka NUC
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Osaka University NUC
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Priority to JP2013556429A priority Critical patent/JP6061872B2/ja
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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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/03—Precipitation; Co-precipitation
    • B01J37/031—Precipitation
    • B01J37/035—Precipitation on carriers
    • 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
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
    • B01J21/063—Titanium; Oxides or hydroxides thereof
    • 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
    • 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
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/70—Catalysts, in general, characterised by their form or physical properties characterised by their crystalline properties, e.g. semi-crystalline
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/08—Heat treatment
    • B01J37/082—Decomposition and pyrolysis
    • B01J37/088—Decomposition of a metal salt
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G23/00—Compounds of titanium
    • C01G23/04—Oxides; Hydroxides
    • C01G23/047—Titanium dioxide
    • C01G23/053—Producing by wet processes, e.g. hydrolysing titanium salts
    • C—CHEMISTRY; METALLURGY
    • C30—CRYSTAL GROWTH
    • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
    • C30B29/10—Inorganic compounds or compositions
    • C30B29/16—Oxides
    • C—CHEMISTRY; METALLURGY
    • C30—CRYSTAL GROWTH
    • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
    • C30B29/60—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape characterised by shape
    • C30B29/605—Products containing multiple oriented crystallites, e.g. columnar crystallites
    • C—CHEMISTRY; METALLURGY
    • C30—CRYSTAL GROWTH
    • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B7/00—Single-crystal growth from solutions using solvents which are liquid at normal temperature, e.g. aqueous solutions
    • C—CHEMISTRY; METALLURGY
    • C30—CRYSTAL GROWTH
    • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B7/00—Single-crystal growth from solutions using solvents which are liquid at normal temperature, e.g. aqueous solutions
    • C30B7/02—Single-crystal growth from solutions using solvents which are liquid at normal temperature, e.g. aqueous solutions by evaporation of the solvent
    • C30B7/04—Single-crystal growth from solutions using solvents which are liquid at normal temperature, e.g. aqueous solutions by evaporation of the solvent using aqueous solvents
    • 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
    • B01J2235/00—Indexing scheme associated with group B01J35/00, related to the analysis techniques used to determine the catalysts form or 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
    • B01J2235/00—Indexing scheme associated with group B01J35/00, related to the analysis techniques used to determine the catalysts form or properties
    • B01J2235/15—X-ray diffraction
    • 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
    • B01J2235/00—Indexing scheme associated with group B01J35/00, related to the analysis techniques used to determine the catalysts form or properties
    • B01J2235/30—Scanning electron microscopy; Transmission electron microscopy
    • 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
    • B01J37/12—Oxidising
    • B01J37/14—Oxidising with gases containing free oxygen
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures

Definitions

  • the present invention relates to a titanium oxide mesocrystal.
  • Titanium oxide particularly chemically stable and highly active anatase titanium oxide (TiO 2 ) nanoparticles, has been widely used in various applications such as photo-water decomposition, environmental purification photocatalysts, and dye-sensitized solar cells. .
  • titanium oxide nanoparticles tend to aggregate randomly, and this contributes to a decrease in photoactivity (photocatalytic activity, etc.), photoenergy conversion efficiency, and the like due to a reduction in surface area and interface mismatch.
  • Non-Patent Documents 1 and 2 In order to solve this problem, development of titanium oxide mesocrystals in which titanium oxide nanoparticles are regularly and densely integrated is underway (see, for example, Non-Patent Documents 1 and 2).
  • the specific surface area is much larger than that of a general titanium oxide nanoparticle (the typical photocatalyst titanium oxide nanoparticle P25 is about 50 m 2 / g). Lower than 10 m 2 / g. Therefore, at present, sufficient photocatalytic activity and the like are not obtained.
  • Non-Patent Document 3 a titanium oxide crystal having a large specific surface area is also known (Non-Patent Document 3), but its size (length) is as small as 450 nm or less. When such a small crystal is used, it tends to aggregate randomly and the photocatalytic activity or the like is lowered as in the case of the titanium oxide nanoparticles, and thus a fundamental solution has not been reached.
  • An object of the present invention is to provide a titanium oxide mesocrystal having a large size and specific surface area. Another object of the present invention is to provide a titanium oxide mesocrystal having excellent photocatalytic activity, photoluminescence characteristics, photoinduced charge separation characteristics, and the like.
  • the present invention includes the following configurations.
  • Item 1 A titanium oxide mesocrystal having a ratio of average width to average thickness (average width / average thickness) of 10 to 100 and a specific surface area of 10 m 2 / g or more.
  • Item 2. Item 2.
  • the titanium oxide mesocrystal according to Item 1 wherein the average width is 3 to 5 ⁇ m.
  • Item 3. Item 3.
  • Item 4. Item 4.
  • the titanium oxide mesocrystal according to any one of Items 1 to 4 which is a single crystal.
  • Item 6. Item 6.
  • TiF 4 , NH 4 NO 3 , NH 4 F and water are contained, the content ratio of TiF 4 and NH 4 NO 3 is 1: 4 to 15 (molar ratio), and TiF 4 and NH 4 F are Item 7.
  • TiF 4 , NH 4 NO 3 , NH 4 F and water are contained, the content ratio of TiF 4 and NH 4 NO 3 is 1: 4 to 15 (molar ratio), and TiF 4 and NH 4 F are An aqueous precursor solution having a content ratio of 1: 1 to 9 (molar ratio) is baked under conditions of 250 to 700 ° C. in an air atmosphere or oxygen atmosphere, and then baked under conditions of 400 to 700 ° C. in an oxygen atmosphere.
  • Item 7. The method for producing a titanium oxide mesocrystal according to any one of Items 1 to 6, comprising a step.
  • Item 10. NH 4 TiOF 3 crystal having a ratio of average width to average thickness (average width / average thickness) of 10 to 100.
  • Item 11. TiF 4 , NH 4 NO 3 , NH 4 F and water are contained, the content ratio of TiF 4 and NH 4 NO 3 is 1: 4 to 15 (molar ratio), and TiF 4 and NH 4 F are Item 11.
  • the method for producing NH 4 TiOF 3 crystal according to Item 10 comprising a step of firing a precursor aqueous solution having a content ratio of 1: 1 to 9 (molar ratio) under a condition of 250 to 300 ° C. in an air atmosphere.
  • the present invention it is possible to provide a titanium oxide mesocrystal having a large size and specific surface area.
  • the specific surface area can be larger than 50 m 2 / g of titanium oxide nanoparticles P25, which is a typical photocatalyst.
  • the titanium oxide mesocrystal of the present invention is excellent in photocatalytic activity, photoluminescence characteristics, photoinduced charge separation characteristics, and the like.
  • N-I, N-II and N-III represent various titanium oxide nanocrystals in which titanium oxide nanoparticles are regularly arranged.
  • M-I, M-II, and M-III represent titanium oxide mesocrystals in which these are regularly arranged.
  • 4 is a graph showing the results of powder X-ray diffraction (XRD) of the crystals of Examples 1 to 3 and Comparative Examples 4, 5, and 11.
  • XRD powder X-ray diffraction
  • peaks of anatase-type titanium oxide, NH 4 NO 3 , and NH 4 TiOF 3 are also shown.
  • 6 is a graph showing the results of powder X-ray diffraction (XRD) of crystals of Comparative Examples 1 and 2. It is a figure which shows the result of the powder X-ray diffraction (XRD) and electron microscope (SEM) observation of the crystal
  • 3 is a graph showing the distribution of thickness of the titanium oxide mesocrystal of Example 2.
  • 6 is a graph showing Cr 6+ photocatalytic reduction activity of crystals of Examples 1 to 4 and Comparative Examples 1 to 3, 5; 6 is a graph showing RhB photocatalytic oxidation activity of crystals of Examples 1 to 4 and Comparative Examples 1 to 3, and 5. It is a conceptual diagram explaining an example of the arrangement
  • FIG. 10 is a graph showing measurement results of time-resolved diffuse reflectance in Comparative Example 2. Is a graph showing the measurement results of a single particle fluorescence spectroscopy in Example 2 and Comparative Example 1. In Example 2, a graph showing the results of measurement of photocurrent response by UV irradiation intensity. Is a graph showing the results of a comparison of the crystal photocurrent response of Example 2 and Comparative Example 1. It is a graph showing a comparison of the photocurrent response by the width and the difference of thickness of the oxide Chitanmeso crystals.
  • FIG. 10 is a diagram showing the results of electron microscope (SEM) observation of the titanium oxide mesocrystal-functional material composite material of Example 8.
  • Titanium oxide mesocrystal of the present invention has a ratio of average width to average thickness (average width / average thickness) of 10 to 100 and a specific surface area of 10 m 2 / g or more.
  • titanium oxide mesocrystal means a crystalline superstructure of mesosize (specifically, about 1 to 10 ⁇ m) in which titanium oxide nanocrystals are regularly arranged.
  • the superstructure means a structure in which nanoparticles or nanocrystals are not randomly aggregated but regularly arranged (see FIG. 1, FIG. 1 of Non-Patent Document 4).
  • N-I, N-II, and N-III represent various titanium oxide nanocrystals in which titanium oxide nanoparticles are regularly arranged.
  • M-I, M-II, and M-III represent titanium oxide mesocrystals in which these are regularly arranged.
  • each titanium oxide nanoparticle is regularly arranged in the titanium oxide mesocrystal.
  • the titanium oxide mesocrystal of the present invention is a large-sized crystal in which the titanium oxide nanocrystals are not randomly aggregated but regularly arranged, and therefore, disordered aggregation can be suppressed.
  • titanium oxide mesocrystal of the present invention since the titanium oxide nanocrystals are regularly arranged as described above, it is possible to form a single crystal as a whole.
  • Amorphous Solid and Polycrystal shown in the lower left represent a state in which titanium oxide nanoparticles or titanium oxide nanocrystals are randomly aggregated.
  • the titanium oxide nanocrystal of the present invention in the conventional disordered aggregate, there are few contacts between the titanium oxide nanocrystals (in FIG. 2, they are in contact only with dots), and electrons generated by sunlight are difficult to conduct.
  • the titanium oxide mesocrystal of the present invention the titanium oxide nanocrystals are regularly arranged, and there are many contact points between the titanium oxide nanocrystals (in FIG. 2, they are in contact with each other), which facilitates conduction of electrons and is high. Electrical conductivity is obtained.
  • the titanium oxide mesocrystal of the present invention can suppress aggregation, it can maintain a high specific surface area compared to the case of using titanium oxide nanoparticles having the same specific surface area, and has a photocatalytic activity. Can be dramatically improved.
  • the width is sufficiently larger than the thickness.
  • the ratio of the average width to the average thickness (average width / average thickness) is about 10 to 100, preferably about 40 to 50.
  • the titanium oxide mesocrystal of the present invention has a large ratio of the average width to the average thickness, and thus can have a ⁇ 001 ⁇ plane having a high surface energy as a main crystal plane. Since the ⁇ 001 ⁇ plane is attracting attention as a highly active crystal plane (Non-Patent Document 5), the titanium oxide mesocrystal of the present invention has a ⁇ 001 ⁇ plane as a main crystal plane, thereby providing photocatalytic activity and the like. Can be improved.
  • the average width is large. Moreover, the one where average thickness is smaller is preferable. Specifically, the average width is preferably about 2 to 8 ⁇ m, more preferably about 4 to 5 ⁇ m. The average thickness is preferably about 50 ⁇ 300 nm, more preferably about 70 ⁇ 110 nm.
  • the average width means an average value of the sides of the estimated square or rectangle when the surface is regarded as a plate crystal having a square or rectangle.
  • the average thickness of the titanium oxide mesocrystal of the present invention is an average value of the thickness in the case of a plate-like crystal, and an average value of the thickness when it is assumed to be a plate-like crystal in the case of not being plate-like.
  • the specific surface area of the titanium oxide mesocrystal of the present invention is 10 m 2 / g or more.
  • the specific surface area of the titanium oxide mesocrystal can be larger than 50 m 2 / g of the titanium oxide nanoparticle P25 which is a typical photocatalyst.
  • the specific surface area of the oxide Chitanmeso crystals is preferably about 10 ⁇ 80m 2 / g, more preferably about 50 ⁇ 70m 2 / g.
  • the specific surface area of the titanium oxide mesocrystal of the present invention can be measured by, for example, the BET method.
  • the titanium oxide nanocrystal constituting the titanium oxide mesocrystal of the present invention may be anatase type or rutile type. Among these, since the catalytic activity is high, the titanium oxide mesocrystal of the present invention is preferably an aggregate of anatase-type titanium oxide nanocrystals.
  • the crystal structure of the titanium oxide nanocrystal can be measured by, for example, powder X-ray diffraction.
  • the average particle diameter of the titanium oxide nanocrystals constituting the titanium oxide mesocrystal of the present invention is preferably about 30 to 70 nm, more preferably about 35 to 40 nm, from the viewpoint of superior photocatalytic activity.
  • the average particle diameter of the titanium oxide nanoparticles can be measured by, for example, powder X-ray diffraction (using Scherrer's equation) or the like.
  • the pore diameter and pore volume in the titanium oxide mesocrystal of the present invention are preferably larger from the viewpoint of further improving the specific surface area.
  • the average pore diameter is preferably about 3 to 8 nm.
  • the average pore volume is preferably about 0.1 to 0.2 cm 3 / g. These can be measured from an adsorption isotherm by the BJH model.
  • the purity of titanium oxide can be improved and a crystal substantially free of impurities such as nitrogen and fluorine can be obtained. This can be confirmed from the fact that the band gap of the titanium oxide mesocrystal of the present invention is comparable to that of titanium oxide.
  • the shape of the titanium oxide mesocrystal of the present invention may be a plate shape or another shape.
  • a plate-like shape is preferable because the ratio of the average width to the average thickness is preferably large.
  • the titanium oxide mesocrystal of the present invention described above can be obtained by a topotactic reaction using the NH 4 TiOF 3 crystal of the present invention as described later.
  • the crystal shape is substantially maintained (see Non-Patent Document 1 etc.), so the crystal shape is the same as that of the titanium oxide mesocrystal of the present invention. Specifically, it is as follows.
  • the NH 4 TiOF 3 crystal of the present invention is characterized by a sufficiently large width compared to the thickness.
  • the ratio of the average width to the average thickness is about 10 to 100, preferably about 40 to 50.
  • the finally obtained titanium oxide mesocrystal is a main crystal with a ⁇ 001 ⁇ plane having a high surface energy. Can have as a face. Since the ⁇ 001 ⁇ plane is attracting attention as a highly active crystal plane (Non-Patent Document 5), the titanium oxide mesocrystal of the present invention has a ⁇ 001 ⁇ plane as a main crystal plane, thereby providing photocatalytic activity and the like. Can be improved.
  • the average width is large. Moreover, the one where average thickness is smaller is preferable. Specifically, the average width is preferably about 2 to 8 ⁇ m, more preferably about 4 to 5 ⁇ m. The average thickness is preferably about 50 ⁇ 300 nm, more preferably about 70 ⁇ 110 nm.
  • the average width and average thickness are those described above.
  • the shape of the NH 4 TiOF 3 crystal of the present invention may be a plate shape or another shape.
  • the ratio of the average width to the average thickness is preferably large, and thus a plate shape is preferable.
  • the titanium oxide mesocrystal of the present invention contains TiF 4 , NH 4 NO 3 , NH 4 F and water, and the content ratio of TiF 4 and NH 4 NO 3 is A precursor aqueous solution having a content ratio of 1: 4 to 15 (molar ratio) and TiF 4 and NH 4 F of 1: 1 to 9 (molar ratio) is 250 to 700 ° C. in an air atmosphere or an oxygen atmosphere. It can be manufactured by a method including a step of baking under conditions of 400 to 700 ° C. in an oxygen atmosphere after baking under conditions.
  • the precursor aqueous solution is fired under conditions of 250 to 700 ° C. in an air atmosphere or an oxygen atmosphere.
  • a liquid layer composed of an aqueous precursor solution may be formed on a substrate and fired under conditions of 250 to 700 ° C. in an air atmosphere or an oxygen atmosphere.
  • the substrate is not particularly limited, and has a smooth surface at room temperature.
  • the surface may be a flat surface or a curved surface, or may be deformed by stress.
  • Specific examples of the substrate which can be used for example, silicon, various kinds of glass, transparent resin or the like. However, since it is necessary to fire at 400 ° C. or higher as described later, it is preferable to use silicon, glass, or the like.
  • the film thickness of the liquid layer is not particularly limited, usually about 2mm or less.
  • the formation method of the liquid layer is not particularly limited, and a known method can be appropriately employed depending on the type of substrate used. For example, deep coating, spin coating, or the like may be performed on the substrate, or a mixed solution of the substrate material and the precursor aqueous solution may be dropped onto silicon, glass, or the like.
  • a functional material can be used to easily manufacture a composite material with the titanium oxide mesocrystal of the present invention.
  • the functional material include tin-doped indium oxide (ITO) and fluorine-doped tin oxide (FTO).
  • TiF 4 is used as the titanium precursor contained in the precursor aqueous solution.
  • F ⁇ ions in TiF 4 are strongly adsorbed on the ⁇ 001 ⁇ plane of the titanium oxide nanocrystal, and a titanium oxide mesocrystal having a ⁇ 001 ⁇ plane as a main crystal plane, that is, a large size is obtained.
  • titanium oxide nanocrystals are not regularly arranged. That is, titanium oxide mesocrystals are not obtained, and only aggregates are obtained.
  • Ti (OC 4 H 9 ) 4 , Ti (SO 4 ) 2 or the like is used as the titanium precursor, only aggregates can be obtained.
  • NH 4 NO 3 is used to control the crystal structure of the titanium oxide mesocrystal.
  • the amount of NH 4 NO 3 used is such that the content ratio of TiF 4 and NH 4 NO 3 is 1: 4 to 15 (molar ratio), preferably 1: 6 to 9 (molar ratio). If the amount of NH 4 NO 3 used is too small, only aggregates of titanium oxide nanoparticles having no crystal structure can be obtained, and titanium oxide mesocrystals cannot be obtained. On the other hand, if the amount of NH 4 NO 3 used is too large, it becomes a mixture of titanium oxide mesocrystals and titanium oxide nanoparticles, and aggregation of titanium oxide nanoparticles cannot be prevented. By setting the amount of NH 4 NO 3 used within the above range, a titanium oxide mesocrystal with higher crystallinity can be obtained.
  • NH 4 F is used to control the size (width) and thickness of the titanium oxide mesocrystal.
  • the amount of NH 4 F used is such that the content ratio of TiF 4 and NH 4 F is 1: 1 to 9 (molar ratio), preferably 1: 3 to 5 (molar ratio). If the amount of NH 4 F used is too small, the average width becomes small and the thickness becomes large, and aggregation cannot be prevented. On the other hand, when the amount of NH 4 F used is too large, the width of the titanium oxide mesocrystal becomes too large, and the thickness becomes too thin and the shape collapses so that aggregation cannot be prevented.
  • water is used as the solvent.
  • an organic solvent can be used.
  • an inorganic solvent is used, and therefore an aqueous solvent, particularly water, is preferable.
  • the amount of water used may be excessive with respect to the other components, but it should not be too much for film formation.
  • the content ratio of TiF 4 and water may be about 1: 100 to 1000 (molar ratio).
  • a titanium oxide mesocrystal is produced by regularly arranging titanium oxide nanocrystals without using a surfactant used in a conventional method (Non-patent Document 1 or the like). Is possible.
  • the precursor aqueous solution described above is first fired under an air atmosphere at 250 to 700 ° C., preferably 250 to 300 ° C., more preferably 250 to 290 ° C. (first firing). .
  • first firing the above-described NH 4 TiOF 3 crystal of the present invention can be manufactured.
  • the NH 4 TiOF 3 crystal of the present invention can be produced even in an oxygen atmosphere.
  • the firing temperature is too low, the mixture of NH 4 NO 3.
  • the firing temperature is too high, a titanium oxide crystal having a specific surface area of 10 m 2 / g or less is obtained.
  • the first firing if the firing is performed at 400 to 700 ° C. in an oxygen atmosphere, the titanium oxide mesocrystal of the present invention can be obtained in one pot without going through the NH 4 TiOF 3 crystal.
  • the produced NH 4 TiOF 3 crystal is fired under a condition of 400 to 700 ° C. in an oxygen atmosphere (second firing).
  • a topotactic reaction (see Non-Patent Document 1, etc.) is caused to obtain the titanium oxide mesocrystal of the present invention.
  • the firing may be performed in the same furnace as in the above-described firing in an air atmosphere or in a different furnace.
  • the titanium oxide mesocrystal of the present invention can be obtained without performing the second firing. .
  • the mixing of impurities such as nitrogen and fluorine into the titanium oxide mesocrystal can be suppressed by setting the atmosphere of the second baking (the first baking when only the first baking is performed) to be an oxygen atmosphere.
  • the oxygen atmosphere is preferably a 100% oxygen gas or a mixed gas atmosphere of oxygen and air having an oxygen concentration of 90% or more.
  • the firing temperature in the second firing is 400 to 700 ° C., preferably 400 to 600 ° C., more preferably 450 to 550 ° C. If the firing temperature is too low, NH 4 TiOF 3 cannot be sufficiently converted to TiO 2, and a titanium oxide mesocrystal cannot be obtained. Further, the specific surface area cannot be increased. On the other hand, if the calcination temperature is too high, titanium oxide mesocrystals can be obtained, but the specific surface area decreases, and the photocatalytic activity and the like deteriorate. Normally, titanium oxide cannot maintain a highly active anatase type when baked at a high temperature, and the structure changes to a rutile type. However, in the present invention, anatase can be baked at a high temperature (near the upper limit of the above temperature range). The mold can be maintained.
  • the titanium oxide mesocrystal of the present invention has a large specific surface area as described above, and is a regular arrangement of titanium oxide nanocrystals, and has a large size and can suppress aggregation, so that photocatalytic activity and photoluminescence characteristics are achieved.
  • the photo-induced charge separation characteristics are high and the conductivity is high.
  • titanium oxide mesocrystals can be produced by a very simple method, the mass productivity is excellent. Therefore, it can be applied to various uses such as an environmental purification photocatalyst, a hydrogen generation photocatalyst, a dye-sensitized solar cell, and a lithium ion battery.
  • Example 2 Firing at 500 ° C. (Meso-TiO 2 -500) An NH 4 TiOF 3 crystal and a titanium oxide mesocrystal of Example 2 were produced in the same manner as in Example 1 except that the firing temperature in an oxygen atmosphere was 500 ° C.
  • Example 3 Firing at 600 ° C. (Meso-TiO 2 -600) An NH 4 TiOF 3 crystal and a titanium oxide mesocrystal of Example 3 were produced in the same manner as in Example 1 except that the firing temperature in an oxygen atmosphere was 600 ° C.
  • Example 4 Firing at 700 ° C. (Meso-TiO 2 -700) An NH 4 TiOF 3 crystal and a titanium oxide mesocrystal of Example 2 were produced in the same manner as in Example 1 except that the firing temperature in an oxygen atmosphere was 700 ° C.
  • Comparative Example 1 Titanium oxide nanocrystals (Nano-TiO 2 ) According to Non-Patent Document 6, a titanium oxide nanocrystal of Comparative Example 1 was produced. This sample was baked at 600 ° C. for 8 hours in an oxygen atmosphere.
  • Comparative Example 3 Titanium oxide microcrystal (Micro-TiO 2 ) In accordance with Non-Patent Document 7, a titanium oxide microcrystal of Comparative Example 3 was produced. This sample was baked at 600 ° C. for 8 hours in an oxygen atmosphere.
  • Comparative Example 4 Firing at 300 ° C. (TiO 2 -300) A titanium oxide crystal of Comparative Example 4 was produced in the same manner as in Example 1 except that the firing temperature in an oxygen atmosphere was 300 ° C.
  • Comparative Example 5 800 ° C. firing (Meso-TiO 2 -800) A titanium oxide crystal of Comparative Example 5 was produced in the same manner as in Example 1 except that the firing temperature in an oxygen atmosphere was 800 ° C.
  • Comparative Example 11 250 ° C. firing (TiO 2 -250) A titanium oxide crystal of Comparative Example 11 was produced in the same manner as in Example 1 except that the firing temperature in an oxygen atmosphere was 250 ° C.
  • Test Example 1 Specific surface area The specific surface areas of the crystals of Examples 1 to 4 and Comparative Examples 1 to 5 were measured by the BET method. The results are shown in Table 1.
  • Test Example 2 Pore diameter and pore volume The pore diameter and pore volume of the crystals of Examples 1 to 4 and Comparative Examples 1 to 5 were measured by the BJH method. The results are shown in Table 1.
  • Test Example 3 X-ray diffraction The characteristics of the crystals of Examples 1 to 3 and Comparative Examples 4, 5 and 11 were measured by powder X-ray diffraction (XRD). For the crystals of Examples 1 to 4 and Comparative Examples 1 to 5, the particle diameter of the titanium oxide nanocrystals constituting each crystal was evaluated from the X-ray diffraction peak using Scherrer's equation. The results are shown in Table 1 and FIG.
  • Test Example 4 Electron Microscope Observation The characteristics of the crystal of Example 2 were observed with a scanning electron microscope (SEM) and a transmission electron microscope (TEM). The results are shown in FIGS.
  • the titanium oxide mesocrystal of the present invention was a plate-like crystal having a substantially square surface.
  • titanium oxide nano crystals were regularly arranged. Further, pores of about several nm were generated. The pore structure was also confirmed by TEM (FIG. 7d), and a single crystal anatase crystal along the ⁇ 001 ⁇ plane was confirmed from the limited-field electron diffraction (SAED) pattern on the crystal. From the high-resolution transmission electron microscope (HRTEM) image of the contact point of the titanium oxide particles, the single crystal lattice showed an atomic plane of anatase (200) or (020) crystal plane having a lattice spacing of about 0.189 nm (FIG. 7e). ).
  • HRTEM transmission electron microscope
  • the average thickness of the titanium oxide mesocrystal was about 80 nm (FIG. 7c), and was distributed in the range of 50 to 300 nm (FIG. 8).
  • Example 5 scanning electron microscope (SEM) images of Example 5 and Comparative Examples 6 to 8 are shown in FIG.
  • SEM scanning electron microscope
  • Examples 6 to 7 can increase the ratio of width to thickness while suppressing aggregation of titanium oxide nanoparticles.
  • Comparative Examples 1 to 3 are also shown in FIGS. 6 (Comparative Example 3), 12 (Comparative Example 1) and 13 (Comparative Example 2). Comparative Examples 1 and 2 are agglomerated, and Comparative Example 3 has a small width to thickness ratio.
  • Test Example 5 Elemental Analysis Elemental analysis of the titanium oxide mesocrystal of Example 2 was performed by energy dispersive X-ray analysis (EDX). As a result, elements other than the constituent elements of titanium oxide such as nitrogen and fluorine were not detected.
  • EDX energy dispersive X-ray analysis
  • the band gap of the titanium oxide mesocrystal of Example 2 was calculated to be 3.2 eV. Since it is almost the same as the band gap of titanium oxide, this also suggests that impurities are not mixed in the titanium oxide mesocrystal of Example 2.
  • Test Example 6 Photocatalytic activity (p-chlorophenol) The photocatalytic oxidation of p-chlorophenol was measured.
  • Example 2 baked at 500 ° C. showed the most excellent photocatalytic activity.
  • Test Example 7 Photocatalytic activity (Cr 6+ ) The photocatalytic reduction of Cr 6+ was measured.
  • Example 2 baked at 500 ° C. showed the most excellent photocatalytic activity.
  • Test Example 8 Photocatalytic activity (RhB) The photocatalytic oxidation of rhodamine B (RhB) was measured.
  • RhB rhodamine B
  • Example 2 baked at 500 ° C. showed the most excellent photocatalytic activity.
  • the crystals of Comparative Examples 1 and 2 have a specific surface area comparable to that of the Examples, but the photocatalytic activity is significantly reduced. This suggests that in the crystal of Comparative Example 1, the titanium oxide nanocrystals are not regularly arranged as in the titanium oxide mesocrystal of the present invention but are randomly aggregated (see FIG. 17).
  • Test Example 9 Time-resolved diffuse reflectance time-resolved reflectance spectroscopy was performed in order to evaluate the lifetime of the charge separation state. This measurement is a criterion for evaluating the efficiency of the photocatalytic reaction.
  • Time-controlled Q-switch Nd 3+ using a delay generator (Stanford Research Systems, DG535): Third high frequency (355 nm, 5 ns (full width at half maximum)) from a YAG laser (Continuum, Surelite II-10), 1.5 mJ / pulse) was used as the excitation light source for titanium oxide.
  • Analytical light from a pulsed 450W xenon arc lamp (Ushio, UXL-451-0) is collected in a focusing lens and directed through a spectrometer (Nikon, G250) to a silicon avalanche photodiode detector (Hamamatsu Photonics, S5343) It was. Transient signals were recorded with an oscilloscope (Tektronix, TDS 580D). All experiments were performed at room temperature.
  • MTPM 4- (methylthio) phenylmethanol
  • Example 2 and Comparative Example 1 are compared, the contribution of adsorption to the reaction efficiency can be minimized.
  • the rate of charge recombination with electrons in titanium oxide can be estimated from the absorption data of the MTPM ⁇ + 550 nm absorption band generated by one-electron oxidation of MTPM adsorbed by photogenerated holes.
  • FIG. 18 these comparisons are made, and the half-life is 2 ⁇ s in Example 2, which is much longer than 0.5 ⁇ s in Comparative Example 1.
  • Similar results were obtained for the titanium oxide mesocrystals of Examples 3 to 4 other than Example 2 (FIG. 20).
  • the crystal of Comparative Example 2 had a very weak transient signal and a very short half-life (FIG. 21).
  • Test Example 10 Single-particle fluorescence spectroscopic light Clear photoluminescence is obtained by recombination of electrons and holes generated. Single particle fluorescence spectroscopy was performed to evaluate the photoluminescence properties of titanium oxide. Fluorescence spectroscopy is a powerful technique that can observe surface reactions with high spatial resolution.
  • Single-particle fluorescence images and emission decay curves were measured with a confocal scanning microscope system (PicoQuant, Micro-Time 200) equipped with an Olympus IX71 inverted fluorescence microscope. Samples were passed through an oil immersion objective lens (Olympus, SAPUPLSAPO 100XO; 1.40 NA, ⁇ 100 ⁇ ) and controlled by a PDL-800B driver (PicoQuant). -W, Inspire Blue TAST-W; 0.8 MHz repetition rate, 10 ⁇ W excitation power). All experiments were performed at room temperature.
  • the intensity weighted average decay lifetime was 5.9 ns at the center and 7.1 ns at the end in the titanium oxide mesocrystal of Example 2.
  • the center part was 6.6 ns and the edge part was 15.2 ns.
  • Comparative Example 1 was about 2.0 ns.
  • Test Example 11 Current Measurement AFM Measurement In order to evaluate the photoinduced charge separation characteristics, current measurement AFM measurement with a UV light source was performed.
  • AFM images and IV curves were obtained with an MFP-3D atomic force microscope (Asylum Research, Santa Barbara, CA) equipped with an ORCA module (Asylum Research, Model 59) attached to an Olympus IX71 inverted fluorescence microscope. . All current measurements were performed using a solid platinum cantilever (25Pt300B; ⁇ ⁇ tip radius less than 20 nm) from Rocky MountainnmNanotechnology, LLC. The electron transport properties were evaluated from IV curves recorded at points marked on the sample surface with or without UV irradiation.
  • the 365 nm light from the LED (OPTO-LINE, MS-LED-365) that passed through the two-color beam splitter (Olympus, DM410) is a neutral density filter (ND filter; Olympus) and an objective lens (Olympus, UPLSAPO 100XO; 1.40 After passing through NA, 100 ⁇ ), the sample was irradiated.
  • Example 2 showed a more remarkable current response to UV irradiation of the same intensity, and It was found that the UV irradiation intensity up to 5 nA may be smaller in Example 2 (FIG. 24). Specifically, when UV of 1.9 mW / cm 2 is irradiated, the photocurrent response is about 1.0 nA in Example 2, about 2.0 nA in Example 4, and about 0.2 in Comparative Example 1. It was 5 nA.
  • Example 2 when the current decay of the crystals of Examples 2 and 4 and Comparative Example 1 after the UV irradiation was stopped was measured, Example 2 was larger than 20 minutes, Example 4 was about 1 minute, and Comparative Example 1 was about 1 minute. 5 minutes, and the titanium oxide mesocrystal of Example 2 was most maintained.
  • Example 8 Titanium oxide mesocrystal-ITO film
  • the precursor aqueous solution was dropped on the substrate.
  • the thickness of the liquid layer was set to 1 mm or less.
  • the liquid layer formed on the ITO substrate was sintered at 400 ° C. for 2 hours in an air atmosphere to form titanium oxide mesocrystals on the silicon substrate.
  • the titanium oxide mesocrystal of Example 1 was formed on the ITO substrate by baking at 400 ° C. for 8 hours in an oxygen atmosphere.

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Abstract

Le rapport de la largeur moyenne à l'épaisseur moyenne (largeur moyenne/épaisseur moyenne) de ce mésocristal d'oxyde de titane est de 10 à 100, et son aire de surface spécifique est de 10 m2/g ou plus. Ainsi, un mésocristal d'oxyde de titane qui a une taille importante et une grande zone de surface spécifique et a une excellente activité photocatalytique, des propriétés de photoluminescence, des propriétés de séparation de charge photoinduite, etc. peut être fourni. Ce mésocristal d'oxyde de titane est obtenu par un procédé qui consiste à cuire une solution de précurseur entre 250 et 700°C dans une atmosphère d'air ou une atmosphère d'oxygène, après quoi la solution est cuite à une température allant de 400 à 700 °C dans une atmosphère d'oxygène, la solution de précurseur comprenant TiF4, NH4NO3, NH4F et de l'eau, le rapport de teneur entre TiF4 et NH4NO3 étant de 1/4 à 15 (rapport molaire) et le rapport de teneur entre TiF4 et NH4F étant de 1/1 à 9 (rapport molaire). Ce mésocristal d'oxyde de titane peut également être obtenu par un procédé qui consiste à cuire la solution de précurseur à une température comprise entre 400 et 700°C dans une atmosphère d'oxygène.
PCT/JP2013/051972 2012-01-31 2013-01-30 Mésocristal d'oxyde de titane Ceased WO2013115213A1 (fr)

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