WO2013176367A1 - 광촉매재, 그 제조 방법 및 광촉매 장치 - Google Patents
광촉매재, 그 제조 방법 및 광촉매 장치 Download PDFInfo
- Publication number
- WO2013176367A1 WO2013176367A1 PCT/KR2012/011572 KR2012011572W WO2013176367A1 WO 2013176367 A1 WO2013176367 A1 WO 2013176367A1 KR 2012011572 W KR2012011572 W KR 2012011572W WO 2013176367 A1 WO2013176367 A1 WO 2013176367A1
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- WIPO (PCT)
- Prior art keywords
- photocatalyst
- metal oxide
- oxide film
- metal
- porous
- Prior art date
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- 239000011941 photocatalyst Substances 0.000 title claims abstract description 81
- 238000004519 manufacturing process Methods 0.000 title claims description 12
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 68
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 68
- 239000002923 metal particle Substances 0.000 claims abstract description 35
- 239000011247 coating layer Substances 0.000 claims description 25
- 238000000034 method Methods 0.000 claims description 21
- 238000004544 sputter deposition Methods 0.000 claims description 18
- 229910052751 metal Inorganic materials 0.000 claims description 17
- 239000002184 metal Substances 0.000 claims description 17
- 239000000758 substrate Substances 0.000 claims description 15
- 239000011230 binding agent Substances 0.000 claims description 11
- 239000012702 metal oxide precursor Substances 0.000 claims description 7
- 239000002002 slurry Substances 0.000 claims description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 6
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 6
- 238000000151 deposition Methods 0.000 claims description 6
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 6
- 239000000843 powder Substances 0.000 claims description 6
- 238000003980 solgel method Methods 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 5
- 230000000844 anti-bacterial effect Effects 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- 239000011261 inert gas Substances 0.000 claims description 4
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 3
- 229910052684 Cerium Inorganic materials 0.000 claims description 3
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 3
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 3
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 3
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 3
- 229910052788 barium Inorganic materials 0.000 claims description 3
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 claims description 3
- 229910052793 cadmium Inorganic materials 0.000 claims description 3
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 claims description 3
- 229910052791 calcium Inorganic materials 0.000 claims description 3
- 239000011575 calcium Substances 0.000 claims description 3
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims description 3
- 229910052804 chromium Inorganic materials 0.000 claims description 3
- 239000011651 chromium Substances 0.000 claims description 3
- 238000004140 cleaning Methods 0.000 claims description 3
- 229910017052 cobalt Inorganic materials 0.000 claims description 3
- 239000010941 cobalt Substances 0.000 claims description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 3
- 229910052802 copper Inorganic materials 0.000 claims description 3
- 239000010949 copper Substances 0.000 claims description 3
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 3
- 229910052737 gold Inorganic materials 0.000 claims description 3
- 239000010931 gold Substances 0.000 claims description 3
- 229910052742 iron Inorganic materials 0.000 claims description 3
- 229910052749 magnesium Inorganic materials 0.000 claims description 3
- 239000011777 magnesium Substances 0.000 claims description 3
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims description 3
- 229910052750 molybdenum Inorganic materials 0.000 claims description 3
- 239000011733 molybdenum Substances 0.000 claims description 3
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- 229910000484 niobium oxide Inorganic materials 0.000 claims description 3
- URLJKFSTXLNXLG-UHFFFAOYSA-N niobium(5+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Nb+5].[Nb+5] URLJKFSTXLNXLG-UHFFFAOYSA-N 0.000 claims description 3
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 claims description 3
- 229910052697 platinum Inorganic materials 0.000 claims description 3
- 229910052709 silver Inorganic materials 0.000 claims description 3
- 239000004332 silver Substances 0.000 claims description 3
- 229910052712 strontium Inorganic materials 0.000 claims description 3
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 claims description 3
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 3
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 3
- 229910052721 tungsten Inorganic materials 0.000 claims description 3
- 239000010937 tungsten Substances 0.000 claims description 3
- 229910001930 tungsten oxide Inorganic materials 0.000 claims description 3
- 229910052720 vanadium Inorganic materials 0.000 claims description 3
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims description 3
- 229910052725 zinc Inorganic materials 0.000 claims description 3
- 239000011701 zinc Substances 0.000 claims description 3
- 239000011787 zinc oxide Substances 0.000 claims description 3
- 238000004332 deodorization Methods 0.000 claims description 2
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 18
- 230000000694 effects Effects 0.000 description 13
- 230000000052 comparative effect Effects 0.000 description 12
- 229910010413 TiO 2 Inorganic materials 0.000 description 7
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 6
- 230000031700 light absorption Effects 0.000 description 6
- 239000000463 material Substances 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- 238000003917 TEM image Methods 0.000 description 4
- 238000009826 distribution Methods 0.000 description 4
- 239000010419 fine particle Substances 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 238000002834 transmittance Methods 0.000 description 3
- HORQAOAYAYGIBM-UHFFFAOYSA-N 2,4-dinitrophenylhydrazine Chemical compound NNC1=CC=C([N+]([O-])=O)C=C1[N+]([O-])=O HORQAOAYAYGIBM-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 230000001877 deodorizing effect Effects 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 230000001699 photocatalysis Effects 0.000 description 2
- -1 superoxide anions Chemical class 0.000 description 2
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- OUUQCZGPVNCOIJ-UHFFFAOYSA-M Superoxide Chemical compound [O-][O] OUUQCZGPVNCOIJ-UHFFFAOYSA-M 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000004703 alkoxides Chemical class 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 239000003256 environmental substance Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- 239000007970 homogeneous dispersion Substances 0.000 description 1
- MVFCKEFYUDZOCX-UHFFFAOYSA-N iron(2+);dinitrate Chemical compound [Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MVFCKEFYUDZOCX-UHFFFAOYSA-N 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical class [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000007581 slurry coating method Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- FYUZFGQCEXHZQV-UHFFFAOYSA-N triethoxy(hydroxy)silane Chemical compound CCO[Si](O)(OCC)OCC FYUZFGQCEXHZQV-UHFFFAOYSA-N 0.000 description 1
- 238000009423 ventilation Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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- 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
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/755—Nickel
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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
- 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
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/391—Physical properties of the active metal ingredient
- B01J35/393—Metal or metal oxide crystallite size
-
- 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
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/613—10-100 m2/g
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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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/615—100-500 m2/g
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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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/66—Pore distribution
-
- 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
- B01J37/341—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
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- 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
Definitions
- a photocatalyst a method for producing the same, and a photocatalyst device.
- Representative photocatalyst material TiO 2 has the advantages of excellent durability and wear resistance, a safe and nontoxic material, and low price.
- the bandgap energy is so large that it can only absorb light below the ultraviolet ray, there is a limit to apply to the room, not the exterior material.
- a visible light responsive photocatalyst having excellent efficiency even in an indoor light source.
- a photocatalyst comprising a porous metal oxide film and metal particles formed on the surface of the porous metal oxide film.
- the photocatalyst has activity against visible light in the wavelength range of about 380 nm to about 700 nm.
- the metal particles may form an island-shaped discontinuous coating layer on the surface of the porous metal oxide film.
- the island shape may have an average diameter of about 1 nm to about 10 nm.
- the thickness of the discontinuous coating layer may be about 0.1nm to about 10nm.
- the metal oxide included in the metal oxide film may include at least one selected from titanium oxide, tungsten oxide, zinc oxide, niobium oxide, and a combination thereof.
- the metal particles are at least selected from tungsten, chromium, vanadium, molybdenum, copper, iron, cobalt, manganese, nickel, platinum, gold, silver, cerium, cadmium, zinc, magnesium, calcium, strontium, barium and combinations thereof. It may comprise one metal.
- the porosity of the porous metal oxide film may be about 5 to about 50%.
- the specific surface area of the porous metal oxide film may be about 50 m 2 / g to about 500 m 2 / g.
- the content of the metal particles may be about 0.0001 mg to about 0.01 mg per 1 cm 2 of the porous metal oxide film plane.
- the metal particles may be included in an amount of about 0.01 wt% to about 10 wt% in 100 wt% of the photocatalyst.
- the step of forming a porous metal oxide film In another embodiment of the invention, the step of forming a porous metal oxide film; And depositing a metal on the surface of the metal oxide film by sputtering to form an island-shaped discontinuous coating layer.
- the metal oxide film may be formed on a substrate by a sol-gel method using a metal oxide precursor, or may be formed by applying a slurry containing a metal oxide powder, a binder, and a solvent to the substrate.
- the heat treatment step is further performed to perform the above-described crystallinity.
- a metal oxide film may be formed or the binder in the metal oxide film may be removed.
- the sputtering method may be performed under an inert gas atmosphere.
- the sputtering method may be performed under a pressure condition of about 3 mTorr to about 10 mTorr.
- the sputtering method may be performed by applying a power of about 100W to about 1000W.
- a photocatalyst device including the photocatalyst is provided.
- the photocatalyst device can be applied to air cleaning, deodorizing or antibacterial applications.
- the photocatalyst responds to visible light and has excellent photocatalytic efficiency.
- FIG. 1 is a 30,000 magnification TEM image of the surface of the coating layer side of the metal particles of the photocatalyst prepared in Example 1.
- Figure 2 is a 100,000-fold TEM image of the surface of the coating layer side of the metal particles of the photocatalyst prepared in Example 1.
- a photocatalyst comprising a porous metal oxide film and metal particles formed on the surface of the porous metal oxide film.
- a material known as a metal oxide used as a photocatalyst may be used without limitation.
- the metal of the metal particles may be doped with the metal oxide, and a metal of a kind capable of imparting activity to visible light by the photocatalyst may be used.
- the metal of the metal particles may be, for example, a transition metal, a noble metal, or the like.
- the photocatalyst may have activity against visible light in the wavelength range of about 380 nm to about 700 nm. Visible light absorption can be calculated as a limit value of the transmittance and reflectance for 100% of the total light, by this calculation method, the photocatalyst according to the present invention specifically, visible light in the range of about 380nm or more to about 700nm or less To about 20% absorption.
- the photocatalyst is a substance capable of purifying air, deodorizing and antibacterial by generating superoxide anion or hydroxy radicals from electrons and holes generated from energy obtained by absorbing light.
- superoxide anions or hydroxy radicals generated from the photocatalyst can decompose harmful environmental substances such as formaldehyde.
- the photocatalyst may have an absorption rate to visible light and thus show excellent efficiency even in an indoor light source, and thus may not require a separate ultraviolet light supply device.
- the metal particles may form an island-shaped discontinuous coating layer on the surface of the porous metal oxide film.
- the island shape may have an average diameter of about 1 nm to about 10 nm, and specifically, about 3 nm to about 8 nm.
- the discontinuous coating layer of the metal particles may be formed by depositing a metal by sputtering. Since the island-shaped diameter is formed to be small as the fine particles as in the above range, the activity efficiency of the photocatalyst to visible light can be further improved. Therefore, preferably, the metal particles may form the discontinuous coating layer as fine particles deposited by the sputtering method.
- the particle size distribution of each island shape or the fine particles of the metal particles may be constant.
- the fine particles of the metal particles having the particle size distribution having a low dispersion degree are deposited and formed, the diameter distribution of each island shape of the discontinuous coating layer also has a low dispersion degree.
- the island-shaped diameter D50 may be about 5 nm or less, and D90 may have a value of about 10 nm or less.
- the photocatalyst is formed on the surface of the porous metal oxide film by coating the surface of the porous metal oxide film by sputtering the metal to dope the metal with the metal oxide to give activity to visible light.
- the metal particles may be evenly distributed on the surface of the porous metal oxide film by sputtering.
- the metal particles may be about 0.0001 mg to about 0.01 mg per 1 cm 2 of the porous metal oxide film plane, and specifically about 0.001 mg to about 0.005 mg.
- the photocatalyst material doped with the metal evenly in the content ratio of the above range may have an excellent activity efficiency for visible light.
- the thickness of the discontinuous coating layer of the metal particles may be about 0.1 nm to about 10 nm.
- the thickness of the discontinuous coating layer of the metal particles is less than the above range, it is difficult to expect visible light activity, and when it exceeds the above range, there is a problem that the light absorption of the metal oxide photocatalyst is not performed smoothly because it is formed as a continuous film. .
- the metal particles may be included in an amount of about 0.01 wt% to about 10 wt% in 100 wt% of the photocatalyst.
- the content of the metal particles is less than the above range, it is difficult to expect the effect by the addition of the metal particles, and when it exceeds the above range may act as an element that inhibits the light absorption into the metal oxide photocatalyst.
- the metal is at least one selected from tungsten, chromium, vanadium, molybdenum, copper, iron, cobalt, manganese, nickel, platinum, gold, silver, cerium, cadmium, zinc, magnesium, calcium, strontium, barium and combinations thereof It may include.
- the metal oxide included in the metal oxide film may include at least one selected from titanium oxide, tungsten oxide, zinc oxide, niobium oxide, and a combination thereof.
- the porosity of the porous metal oxide film may be about 5 to about 50%. When the porosity is in the above range, the photocatalyst may have better activity efficiency for visible light. If the porous metal oxide film does not have porosity and is densely formed by a sputtering method or the like, adsorption of reactants such as formaldehyde is not efficiently performed, so it is difficult to expect excellent photocatalytic activity.
- the specific surface area of the porous metal oxide film may be about 50 m 2 / g to about 500 m 2 / g. In the case of having a specific surface area in the above range, the photocatalyst may have better activity efficiency against visible light.
- the step of forming a porous metal oxide film In another embodiment of the invention, the step of forming a porous metal oxide film; And depositing a metal on the surface of the metal oxide film by sputtering to form an island-shaped discontinuous coating layer on the surface of the metal oxide film.
- the above-described photocatalyst may be manufactured according to the photocatalyst manufacturing method.
- the porous metal oxide film may be formed on a substrate by a solution method.
- the substrate may be a glass substrate.
- the metal oxide film may be deposited on a substrate by a sol-gel method using a metal oxide precursor.
- a solution containing a metal oxide precursor may be coated in a sol form, dried to form a gel, and then subjected to a heat treatment step to form a film having crystallinity.
- a solution containing the metal oxide precursor such as metal alkoxide, alcohol, acid, etc. may be prepared and then hydrolyzed, and a sol may be obtained by dehydration and dealcohol, and then coated on a flat substrate.
- the sol-gel method may be carried out according to known process conditions, and is not limited to specific conditions.
- a slurry comprising a metal oxide powder, a binder, and a solvent may be applied to a substrate to form a film.
- Specific process conditions for forming a metal oxide film by such a slurry coating method may also be carried out as known, and are not limited to specific conditions.
- the binder is used to fix the metal oxide on the substrate, and for example, resin may be used as the binder, and the binder may be applied to the substrate, followed by heat treatment to remove the binder.
- the sputtering method may be performed for several seconds to several minutes by applying a power of 200W to 1000W under a pressure condition of about 1 to about 10m Torr under an inert gas atmosphere such as argon.
- the photocatalyst manufacturing method has the advantage of uniform coating on a large area substrate, since the metal is deposited by sputtering to form a discontinuous coating layer on the porous metal oxide film, and the metal particles are uniform in nano size. Can be dispersed to form a coating layer.
- the photocatalyst produced by such a photocatalyst production method can further improve activity against visible light.
- a photocatalyst device including the photocatalyst is provided.
- the photocatalyst device may be manufactured, for example, as a device for air cleaning, deodorization, and antibacterial use.
- Degussa P25 was used as TiO 2 .
- P25 was dispersed in isopropanol to prepare a P25 isopropanol slurry at a concentration of 5 wt%.
- the slurry was treated with a homogenizer for 30 minutes to obtain a homogeneous dispersion. It was coated on 0.7t Na-free glass.
- the coating amount was set to 1 g / m 2 based on P25.
- Sputtering was performed on the TiO 2 coated glass to form a discontinuous island-shaped Ag coating layer.
- an Ag / TiO 2 photocatalyst was prepared.
- the metal oxide of the prepared photocatalyst had a porosity of about 20% and a specific surface area of about 56m 2 / g, the content of Ag metal particles in the photocatalyst was 0.6wt%, and the content of Ag metal particles per porous metal oxide (TiO 2 ) film plane. 0.0026 mg / cm 2 .
- the thickness of the island-shaped Ag coating layer is 1 nm as measured by TEM (JEOL, JEM-2010).
- An Ag / WO 3 photocatalyst was prepared in the same manner as in Example 1 except that WO 3 powder (Aldrich) was used instead of TiO 2 .
- the metal oxide of the prepared photocatalyst had a porosity of about 20% and a specific surface area of about 52 m 2 / g, the content of Ag metal particles in the photocatalyst was 0.4wt%, and the content of Ag metal particles per plane of the porous metal oxide (WO 3 ) film was 0.0026 mg / cm 2 .
- the thickness of the island-shaped Ag coating layer is about 1 nm as measured by TEM (JEOL, JEM-2010).
- Example 1 a TiO 2 porous membrane was prepared without forming an Ag coating layer, thereby preparing a photocatalyst.
- Example 2 a photocatalyst was prepared by preparing a WO 3 porous membrane without forming an Ag coating layer.
- FIG. 1 is a 30000 magnification TEM image of the Ag coating layer side surface of the photocatalyst prepared in Example 1
- Figure 2 is a 100000 magnification TEM image of the Ag coating layer side surface of the photocatalyst prepared in Example 1. It can be seen from FIG. 1 and FIG. 2 that the diameter of the metal particles formed on the porous metal oxide surface is about 5 nm on average.
- the ultraviolet and visible light absorption rates of the photocatalysts prepared in Examples 1 and 2 and Comparative Examples 1 and 2 were evaluated.
- the wavelength was measured in the range of 300 nm to 780 nm, and the limit values of the transmittance and the reflectance for the 100% total light were calculated as the absorbance.
- Figure 3 shows the results of calculating the ultraviolet and visible light absorption from the results of measuring the transmittance and reflectance of the photocatalysts of Examples 1 and 2 and Comparative Examples 1 and 2 using Shimadzu's Solidspec-3700 model. .
- Formaldehyde removal performance of the photocatalysts of Example 1 and Comparative Example 3 was evaluated. After installing the photocatalyst coated glass (165mmX165mmX0.7mm) produced in Example 1 and Comparative Example 3 in a 20L small chamber (ADTEC Co.), clean air having a formaldehyde concentration of 0.08 ppm was flown at a flow rate of 167 cc / min. Continuous flow was made so that the number of ventilation was 0.5 times / hr. A 10W white fluorescent lamp was used as the light source, and the illuminance was set to be 1000 lux. Formaldehyde removal rate was calculated by measuring the concentration before entering the chamber and after passing through the chamber is shown in Table 1 below. The concentration was analyzed by HPLC (Agilent) by concentrating the amount for 10 L using a DNPH (2,4-dinitrophenylhydrazine) cartridge.
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Abstract
Description
구분 | 포름알데히드 제거율 |
실시예 1 | 81% |
실시예 2 | 85% |
비교예 1 | 0 |
비교예 2 | 0 |
비교예 3 | 0% |
Claims (19)
- 다공성 금속 산화물막; 및상기 다공성 금속 산화물막의 표면에 형성된 금속 입자;를 포함하는 광촉매재.
- 제1항에 있어서,380nm 내지 700nm 파장범위의 가시광선에 대하여 활성을 갖는광촉매재.
- 제1항에 있어서,상기 금속 입자는 상기 다공성 금속 산화물막의 표면에 아일랜드 형상의 불연속 코팅층을 형성하는광촉매재.
- 제3항에 있어서,상기 아일랜드 형상은 평균 직경이 1nm 내지 10nm인광촉매재.
- 제3항에 있어서,상기 불연속 코팅층의 두께가 0.1nm 내지 10nm인광촉매재.
- 제1항에 있어서,상기 금속 산화물막에 포함된 금속 산화물은 산화티탄, 산화텅스텐, 산화아연, 산화니오븀 및 이들의 조합에서 선택된 적어도 하나를 포함하는광촉매재.
- 제1항에 있어서,상기 금속 입자는 텅스텐, 크롬, 바나듐, 몰리브데넘, 구리, 철, 코발트, 망간, 니켈, 백금, 금, 은, 세륨, 카드늄, 아연, 마그네슘, 칼슘, 스트론튬, 바륨 및 이들의 조합에서 선택된 적어도 하나의 금속을 포함하는광촉매재.
- 제1항에 있어서,상기 다공성 금속 산화물막의 기공도는 5 내지 50%인광촉매재.
- 제1항에 있어서,상기 다공성 금속 산화물막의 비표면적이 50m2/g 내지 500m2/g인광촉매재.
- 제1항에 있어서,상기 금속 입자의 함량은 상기 다공성 금속 산화물막 평면 1㎠당 0.0001mg 내지 0.01mg인광촉매재.
- 제1항에 있어서,상기 금속 입자는 상기 광촉매재 100wt% 중 0.01wt% 내지 10wt% 함량으로 포함된광촉매재.
- 다공성 금속 산화물막을 성막하는 단계; 및상기 금속 산화물막 표면에 금속을 스퍼터링법에 의해 증착하여 아일랜드 형상의 불연속 코팅층을 형성하는 단계를 포함하는 광촉매재 제조 방법.
- 제12항에 있어서,상기 금속 산화물막은 금속 산화물 전구체를 이용하는 졸겔법에 의해 기판 상에 성막되거나, 또는 금속 산화물 분말, 바인더 및 용매를 포함하는 슬러리를 기판에 도포하여 성막되는광촉매재 제조 방법.
- 제12항에 있어서,상기 금속 산화물막이 금속 산화물 전구체를 이용하는 졸겔법에 의해 기판 상에 성막된 후, 또는 금속 산화물 분말, 바인더 및 용매를 포함하는 슬러리를 도포하여 성막된 후, 열처리 단계를 더 수행하여 결정성을 갖는 상기 금속 산화물막을 형성하거나, 또는 상기 금속 산화물막 내의 상기 바인더를 제거하는광촉매재 제조 방법.
- 제12항에 있어서,상기 스퍼터링법은 불활성 가스 분위기 하에서 수행되는광촉매재 제조 방법.
- 제12항에 있어서,상기 스퍼터링법은 3 mTorr 내지 10 mTorr 압력 조건 하에서 수행되는광촉매재 제조 방법.
- 제12항에 있어서,상기 스퍼터링법은 100W 내지 1000W의 전력을 인가하여 수행되는광촉매재 제조 방법.
- 제1항 내지 제11항 중 어느 한 항에 따른 광촉매재를 포함하는 광촉매 장치.
- 제18항에 있어서,공기청정, 탈취 또는 항균 용도에 적용되는광촉매 장치.
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CN201280073270.4A CN104302398A (zh) | 2012-05-25 | 2012-12-27 | 光催化剂,该光催化剂的制备方法及光催化剂装置 |
US14/400,641 US9636660B2 (en) | 2012-05-25 | 2012-12-27 | Photocatalyst, manufacturing method therefor, and photocatalyst apparatus |
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WO2016040667A1 (en) * | 2014-09-10 | 2016-03-17 | Nitto Denko Corporation | Improved air purification system and method for removing formaldehyde |
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KR101942261B1 (ko) * | 2014-09-24 | 2019-01-28 | (주)엘지하우시스 | 가시광 활성 광촉매 타일 |
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KR101946383B1 (ko) * | 2015-09-14 | 2019-02-12 | (주)엘지하우시스 | 광촉매 기능성 부직포 및 이의 제조방법 |
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KR101465299B1 (ko) | 2014-12-04 |
US20150099621A1 (en) | 2015-04-09 |
JP2015522406A (ja) | 2015-08-06 |
KR20130132051A (ko) | 2013-12-04 |
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TWI457177B (zh) | 2014-10-21 |
US9636660B2 (en) | 2017-05-02 |
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