TWI457177B - 光催化劑及其製備方法及光催化劑裝置 - Google Patents
光催化劑及其製備方法及光催化劑裝置 Download PDFInfo
- Publication number
- TWI457177B TWI457177B TW102118423A TW102118423A TWI457177B TW I457177 B TWI457177 B TW I457177B TW 102118423 A TW102118423 A TW 102118423A TW 102118423 A TW102118423 A TW 102118423A TW I457177 B TWI457177 B TW I457177B
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- Prior art keywords
- metal oxide
- photocatalyst
- oxide film
- porous metal
- photocatalyst according
- Prior art date
Links
- 239000011941 photocatalyst Substances 0.000 title claims description 82
- 238000000034 method Methods 0.000 title description 12
- 229910044991 metal oxide Inorganic materials 0.000 claims description 70
- 150000004706 metal oxides Chemical class 0.000 claims description 70
- 239000002923 metal particle Substances 0.000 claims description 34
- 239000011247 coating layer Substances 0.000 claims description 21
- 229910052751 metal Inorganic materials 0.000 claims description 19
- 239000002184 metal Substances 0.000 claims description 19
- 238000004544 sputter deposition Methods 0.000 claims description 18
- 239000000758 substrate Substances 0.000 claims description 15
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 14
- 229910052709 silver Inorganic materials 0.000 claims description 14
- 239000004332 silver Substances 0.000 claims description 14
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 10
- 239000011230 binding agent Substances 0.000 claims description 10
- 238000004519 manufacturing process Methods 0.000 claims description 8
- 239000002002 slurry Substances 0.000 claims description 8
- 239000002904 solvent 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
- 239000012702 metal oxide precursor Substances 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
- 238000004887 air purification Methods 0.000 claims description 4
- 230000000844 anti-bacterial effect Effects 0.000 claims description 4
- 238000004332 deodorization Methods 0.000 claims description 4
- 239000011261 inert gas Substances 0.000 claims description 4
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 4
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 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
- 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
- 229910000420 cerium oxide Inorganic materials 0.000 claims description 3
- 229910052804 chromium Inorganic materials 0.000 claims description 3
- 239000011651 chromium Substances 0.000 claims description 3
- 238000000576 coating method 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
- 238000000151 deposition Methods 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
- 238000010438 heat treatment Methods 0.000 claims description 3
- 229910052742 iron Inorganic materials 0.000 claims description 3
- 229910052746 lanthanum Inorganic materials 0.000 claims description 3
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 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
- 239000000463 material Substances 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
- 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
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 claims description 3
- 229910052697 platinum Inorganic materials 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
- 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
- 239000011248 coating agent Substances 0.000 claims 2
- 239000010410 layer Substances 0.000 claims 1
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 9
- 230000000694 effects Effects 0.000 description 8
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 7
- 239000011521 glass Substances 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 4
- 230000005540 biological transmission Effects 0.000 description 4
- 239000006185 dispersion Substances 0.000 description 4
- 238000009826 distribution Methods 0.000 description 4
- ZNOKGRXACCSDPY-UHFFFAOYSA-N tungsten trioxide Chemical compound O=[W](=O)=O ZNOKGRXACCSDPY-UHFFFAOYSA-N 0.000 description 4
- 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 3
- 239000010419 fine particle Substances 0.000 description 3
- 230000001699 photocatalysis Effects 0.000 description 3
- 238000002834 transmittance Methods 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000004128 high performance liquid chromatography Methods 0.000 description 2
- TUJKJAMUKRIRHC-UHFFFAOYSA-N hydroxyl Chemical compound [OH] TUJKJAMUKRIRHC-UHFFFAOYSA-N 0.000 description 2
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- -1 peroxide anion Chemical class 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 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 2
- 238000007740 vapor deposition Methods 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
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000004703 alkoxides Chemical class 0.000 description 1
- 239000003054 catalyst Substances 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
- 239000012153 distilled water Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000003256 environmental substance Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 239000000203 mixture Substances 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
- 239000011148 porous material Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000002360 preparation method Methods 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
- 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
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
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- 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
- B01J23/683—Silver or gold with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum or tungsten
- B01J23/687—Silver or gold with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum or tungsten with tungsten
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- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
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- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
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- B01J23/02—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the alkali- or alkaline earth metals or beryllium
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- B01J23/04—Alkali metals
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- B01J23/10—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of rare earths
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- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/20—Vanadium, niobium or tantalum
- B01J23/22—Vanadium
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- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/24—Chromium, molybdenum or tungsten
- B01J23/26—Chromium
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- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/24—Chromium, molybdenum or tungsten
- B01J23/28—Molybdenum
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- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/24—Chromium, molybdenum or tungsten
- B01J23/30—Tungsten
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- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/32—Manganese, technetium or rhenium
- B01J23/34—Manganese
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/42—Platinum
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
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- B01J23/48—Silver or gold
- B01J23/50—Silver
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- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
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- B—PERFORMING OPERATIONS; TRANSPORTING
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Description
本發明涉及光催化劑及其製備方法及該光催化劑裝置。
二氧化鈦(TiO2
)作為代表性的光催化物質,是耐久性優秀、耐磨性優秀、安全無毒的物質,具有價格低廉的優點。另一方面,由於帶隙能量大,只吸收紫外線以下的光,因而在適用於非外置材料的室內方面存在限度。
基於這種層面,對以用於室內為目的、能夠吸收可視光的、對可使可視光具有活性的催化劑進行了很多研究。但是,在許多研究事例中很難找到一貫的傾向,尤其,很難找到在實際居住條件下性能得到驗證的結果。
本發明的一實例的目的在於,提供一種在室內光源下也具有優秀效率的可視光回應型光催化劑。
本發明的再一實施例的目的在於,提供一種製備上述光催化劑的方法。
本發明的另一實施例的目的在於,提供一種利用上述光催化劑的光催化劑裝置。
本發明的一實施例提供一種包含多孔性金屬氧化物膜及形成於上述多孔性金屬氧化物膜的表面的金屬粒子的光催化劑。
上述光催化劑對波長在約380nm至約700nm範圍的可視光具有活性。
上述金屬粒子能夠在上述多孔性金屬氧化物膜的表面形成島形狀的不連續的塗敷層。
上述島形狀的平均直徑可為約1nm至約10nm。
上述不連續的塗敷層的厚度可為約0.1nm至約10nm。
包含在上述多孔性金屬氧化物膜的金屬氧化物可包含選自氧化鈦、氧化鎢、氧化鋅、氧化鈮及它們的組合中的至少一種。
上述金屬粒子可包含選自鎢、鉻、釩、鉬、銅、鐵、鈷、錳、鎳、鉑、金、銀、鈰、鎘、鋅、鎂、鈣、鍶、鋇及它們的組合中的至少一種金屬。
上述多孔性金屬氧化物膜的孔隙度可為約5%至約50%。
上述多孔性金屬氧化物膜的比表面積可為約50m2
/g至約500m2
/g。
每1cm2
上述多孔性金屬氧化物膜平面包含約0.0001mg至約0.01mg的上述金屬粒子。
在上述光催化劑100wt%中,可包含0.01wt%至10wt%含量的上述金屬粒子。
本發明的再一實例提供一種光催化劑的製備方法,其特徵在
於,包括如下步驟:使多孔性金屬氧化物膜成膜的步驟;以及通過濺射法在上述多孔性金屬氧化物膜的表面蒸鍍金屬來形成島形狀的不連續的塗敷層的步驟。
根據利用金屬氧化物前驅體的溶膠-凝膠法,使上述多孔性金屬氧化物膜成膜於基板上,或者可將包含金屬氧化物粉末、粘結劑及溶劑的漿料塗敷於基板來使上述多孔性金屬氧化物膜成膜。
在根據利用金屬氧化物前驅體的溶膠-凝膠法,使上述多孔性金屬氧化物膜成膜於基板上後,或者在塗敷包含金屬氧化物粉末、粘結劑及溶劑的漿料來使上述多孔性金屬氧化物膜成膜之後,還可進行熱處理步驟來形成具有結晶性的上述多孔性金屬氧化物膜,或者可去除上述多孔性金屬氧化物膜內的上述粘結劑。
上述濺射法可在非活性氣體氛圍下執行。
上述濺射法可在約3mTorr至約10mTorr的壓力條件下執行。
上述濺射法可通過施加約100W至約1000W的電力來執行。
本發明的另一實例提供一種包括上述光催化劑的光催化劑裝置。
上述光催化劑裝置可適用於空氣淨化、除臭或者抗菌用途上。
上述光催化劑對可見光進行回應,並具有優秀的光催化效率。
第1圖為本發明實施例1中製備的光催化劑的金屬粒子的塗敷層側表面的30000倍率透射電子顯微鏡(TEM)之圖示。
第2圖為本發明實施例1中製備的光催化劑的金屬粒子的塗敷層側表面的100000倍率透射電子顯微鏡(TEM)的圖示。
第3圖為實施例1至實施例2及比較例1至比較例2的光催化劑的紫外線吸收率及可見光的吸收率的曲線圖。
以下,對本發明的實例進行詳細說明。但,這只是例示性的,本發明不被此所限制,本發明僅根據所附的申請專利範圍來定義。
本發明的一實例提供一種包含多孔性金屬氧化物膜及形成於上述多孔性金屬氧化物膜的表面的金屬粒子的光催化劑。形成上述多孔性金屬氧化物膜的金屬氧化物可不受限制地使用作為光催化劑使用的作為金屬氧化物所公知的物質。上述金屬粒子的金屬可使用摻雜於上述金屬氧化物來能夠賦予上述光催化劑對可見光的活性的種類的金屬。上述金屬粒子的金屬,例如,可以是過渡金屬、貴金屬等。
上述光催化劑可對波長在約380nm至約700nm範圍的可見光具有活性。可見光吸收率可通過對100%的全部光除於透射率與反射率的值來計算,並且,根據這種計算方式,本發明的光催化劑,具體地,能夠以約2%至約20%的吸收率吸收波長在約380nm以上至約700nm以下範圍的可見光。
上述光催化劑是一種從吸收光而得到的能量中生成的電子與空穴生成過氧化物負離子或者羥自由基等,來能夠起到空氣淨化、除臭、抗菌作用的物質。例如,從上述光催化劑生成的過氧化物負離子或者羥自由基能夠分解如甲醛等的有害環境物質。另一方面,由於上述光催化劑對可見光具有吸收率,在室內光源下也表現出優秀的效率,因而可不需要額
外的紫外線供給裝置。
上述金屬粒子可在上述多孔性金屬氧化物膜的表面形成島形狀的不連續的塗敷層。上述島形狀的平均直徑可為約1nm至約10nm,具體地,平均直徑可為約3nm至約8nm。上述金屬粒子的不連續的塗敷層可根據濺射法蒸鍍金屬來形成。通過使上述島形狀的直徑如同上述範圍形成小的微粒,能夠更加提高上述光催化劑對可見光的活性效率。因此,優選地,上述金屬粒子為根據濺射法來蒸鍍的微粒,能夠形成上述不連續的塗敷層。並且,由於通過濺射法形成上述金屬粒子的不連續的塗敷層,因而各島形狀或者金屬粒子的微粒的粒徑分佈能夠穩定。由於像這樣蒸鍍形成具有分散度低的粒徑分佈的金屬粒子的微粒,因而上述不連續的塗敷層的各島形狀的直徑分佈的分散度也低。例如,上述島形狀的直徑的D50可具有約5nm以下的值,D90可具有約10nm以下的值。在具有上述範圍的分佈度的情況下,上述光催化劑對可見光的活性效率能夠更加優秀。
如此地,上述光催化劑為了賦予對可見光的活性,為了將上述金屬摻雜於上述金屬氧化物,根據濺射法將上述金屬塗敷於上述多孔性金屬氧化物膜的表面,使得上述金屬粒子形成於多孔性金屬氧化物膜表面。這時,如上所述,可根據濺射法使上述金屬粒子均勻地分佈在多孔性金屬氧化物膜的表面。此時,如上所述,可以通過濺射法分佈成使上述金屬粒子均勻地分散在多孔性金屬氧化物膜的表面。例如,每1cm2
上述多孔性金屬氧化物膜平面包含約0.0001mg至約0.01mg的上述金屬粒子,具體地,每1cm2
上述多孔性金屬氧化物膜平面包含約0.001mg至約0.005mg上述金屬粒子。由上述範圍的含量比均勻摻雜上述金屬的上述光催化劑對可見光的活性效率能夠更加優秀。
上述金屬粒子的上述不連續的塗敷層的厚度可為約0.1nm至
約10nm。
例如,在100wt%的上述光催化劑中,可包含約0.01wt%至約10wt%含量的上述金屬粒子。
上述金屬可包括選自鎢、鉻、釩、鉬、銅、鐵、鈷、錳、鎳、鉑、金、銀、鈰、鎘、鋅、鎂、鈣、鍶、鋇及它們的組合中的至少一種。
包含在上述多孔性金屬氧化物膜的金屬氧化物可包括選自氧化鈦、氧化鎢、氧化鋅、氧化鈮及它們的組合中的至少一種。
上述多孔性金屬氧化物膜的孔隙度可為約5%至約50%。如果上述多孔性金屬氧化物膜具有上述範圍的孔隙度,則上述光催化劑對可見光的活性效率能夠更加優秀。如果,多孔性金屬氧化物膜根據濺射方法等,周密地形成而不具有孔隙,則很難有效地吸附甲醛等反應物,導致難以期待優秀的光催化活性。
上述多孔性金屬氧化物膜的比表面積可為約50m2
/g至約500m2
/g。如果上述多孔性金屬氧化物膜具有上述範圍的比表面積,則上述光催化劑對可見光的活性效率能夠更加優秀。
在本發明的另一實例,提供一種光催化劑的製備方法,其包括如下步驟:使多孔性金屬氧化物膜成膜的步驟;以及通過濺射法在上述多孔性金屬氧化物膜的表面蒸鍍金屬來在上述多孔性金屬氧化物膜的表面形成島形狀的不連續的塗敷層的步驟。
可根據上述光催化劑的製備方法來製備出如上所述的光催化劑。
為了使上述多孔性金屬氧化物膜成膜,例如,可利用溶劑法在基板上形成上述多孔性金屬氧化物膜。並且,例如,上述基板可使用玻
璃基板。
在一實例中,可根據利用金屬氧化物的前驅體的溶膠-凝膠法,使上述多孔性金屬氧化物膜成膜於基板上。具體地,可在以溶膠形態塗敷包含金屬氧化物前驅體的溶劑之後,進行乾燥以凝膠狀成膜,之後執行熱處理步驟來形成具有結晶性的膜。例如,準備如金屬醇鹽等的包含上述金屬氧化物前驅體、乙醇、酸等的溶液後進行水解,並且通過脫水、脫乙醇得到溶膠狀態後,就能夠塗敷於平板型基板。上述溶膠-凝膠法可根據公知的工序條件來執行,不受特定條件的限制。
在再一實例中,首先,可通過將包含金屬氧化物粉末、粘結劑及溶劑的漿料塗敷於基板上來成膜。根據這種漿料塗敷法來形成多孔性金屬氧化物膜的具體的工序條件也可根據公知條件來執行,不受特定條件的限制。上述粘結劑是用於將金屬氧化物固定於基板上的,例如,可將樹脂用作粘結劑來使用,且可在基板上塗敷漿料後進行熱處理來去除上述粘結劑。
具體地,上述濺射法可在氬等的非活性氣體氛圍下,以及約1mTorr至約10mTorr的工序壓力條件下,施加200W至1000W的電力來執行數秒鐘至數分鐘。
上述光催化劑的製備方法由於根據濺射法蒸鍍上述金屬來在上述多孔性金屬氧化物膜形成不連續的塗敷層,因而上述光催化劑的製備方法具有能夠對大面積基板均勻地塗敷的優點,並且能夠使上述金屬粒子以奈米大小均勻分散來形成塗敷層。根據這種光催化劑的製備方法製備的光催化劑,能夠更加提高對可見光的活性。
在本發明的另一實例中,提供一種包含上述光催化劑的光催化劑裝置。上述光催化劑裝置,例如,可製備成空氣淨化、除臭、抗菌用
途的裝置。
以下,記載本發明的實施例以及比較例。但是,這種下述的實施例只是本發明的一實施例,而本發明並不限定於下述的實施例。
作為二氧化鈦(TiO2
),使用了德固薩(Degussa)的P25。將P25分散於異丙醇,製備出濃度為5wt%的P25異丙醇漿料。用均質器(Homogenizer)對上述漿料進行30分鐘處理後,得到了均勻分散液。將此分散液塗敷於不含Na(Na-free)的0.7t的玻璃。使塗敷量以P25基準成為1g/m2
。對塗敷有上述二氧化鈦(TiO2
)的玻璃進行濺射來形成了不連續的島形狀的銀(Ag)塗敷層。作為靶使用了銀(Ag)金屬,工序壓力為3mTorr、直流(DC)電力為500W,並且作為非活性氣體注入了100cc/min的氬氣,蒸鍍了5秒鐘。以上述方法製備了銀(Ag)/二氧化鈦(TiO2
)光催化劑。所製備的光催化劑的金屬氧化物的孔隙度為約20%、比表面積為約56m2
/g,並且銀(Ag)金屬粒子中的光催化劑的含量為0.6wt%,每平面的多孔性金屬氧化物(TiO2
)膜的銀(Ag)金屬粒子含量為0.0026mg/cm2
。
除了使用三氧化鎢(WO3
)粉末(Aldrich)來代替二氧化鈦(TiO2)之外,以與實施例1相同的方法製備出Ag/WO3
光催化劑。所製備的光催化劑的金屬氧化物的孔隙度為約20%、比表面積為約52m2
/g,並且光催化劑中的銀(Ag)金屬粒子的含量為0.4wt%、每平面的多孔性金屬氧化物(WO3
)膜的銀(Ag)金屬粒子的含量為0.0026mg/cm2
。
在實施例1中不形成銀(Ag)塗敷層來製備出二氧化鈦(TiO2
)多孔性膜來製備了光催化劑。
實施例2中不形成銀(Ag)塗敷層來製備出三氧化鎢(WO3
)多孔性膜來製備了光催化劑。
在第一反應器中放入四異丙醇鈦142g、異丙醇72g和二乙醯基甲烷10g,並在常溫下進行了30分鐘的反應。在第二反應器中放入蒸餾水760g、硝酸鐵1.4g、硝酸鋅2.6g、硝酸銅1.8g後以400rpm進行攪拌,使金屬鹽完全溶解。慢慢向上述第二反應器投入上述第一反應器的溶液後滴下(dropping)1.6g的硝酸,再將溫度升溫至80℃後,進行了3小時的反應。最後,投入7.6g的正矽酸三乙酯(triethyl orthosilicate),進行了1小時的反應,製備出透明的可見光活性二氧化鈦類光催化劑。
第1圖是在上述實施例1中製備的光催化劑的銀(Ag)塗敷層側表面的30000倍率透射電子顯微鏡(TEM)圖像,第2圖是在實施例1中製備的光催化劑的銀(Ag)塗敷層側表面的100000倍率透射電子顯微鏡(TEM)圖像。通過第1圖及第2圖能夠確認形成於多孔性金屬氧化物表面的金屬粒子的平均直徑大小為約5nm。
對實施例1至實施例2及比較例1至比較例2中製備的光催化劑,評價了基於波長的紫外線吸收率及可見光吸收率。在300nm至780nm的波長範圍內進行了測量,以對100%的全部光除於透射率與反射率的值作為
吸收率來進行了計算。
第3圖圖示出根據利用島津(Shimadzu)公司的Solidspec-3700型號,由上述實施例1至實施例2及比較例1至比較例2的光催化劑的透射率與反射率的測量結果計算出紫外線的吸收率及可見光的吸收率的結果。
對實施例1及比較例3的光催化劑評價了去除甲醛的性能。將在實施例1及比較例3中製備的塗敷有光催化劑的玻璃(165mm×165mm×0.7mm)設置在20L的小型腔體(ADTEC社:進達科貿易(深圳)有限公司產品)內,然後以167cc/min的流量持續向腔體內流入甲醛濃度為0.08ppm的淨化空氣,且使換氣次數達到0.5次/hr。作為光源使用了10W的白色螢光燈,且將照度設成1000勒克斯(lux)。測量淨化空氣進入腔體之前的濃度與通過腔體後的濃度來計算了甲醛去除率,並記錄到下表1。利用2,4-二硝基苯肼(DNPH,2,4-dinitrophenylhydrazine)暗盒濃縮相對於10L的量,再利用高性能高效液相色譜法(HPLC,Agilent安捷倫公司產品)分析了濃度。
Claims (19)
- 一種光催化劑,包括:多孔性金屬氧化物膜;以及金屬粒子,形成於該多孔性金屬氧化物膜的表面。
- 根據申請專利範圍第1項所述的光催化劑,其中,對波長在380nm至700nm範圍內的可見光具有活性。
- 根據申請專利範圍第1項所述的光催化劑,其中,該金屬粒子在該多孔性金屬氧化物膜的表面形成島形狀的不連續的塗敷層。
- 根據申請專利範圍第3項所述的光催化劑,其中,該島形狀的平均直徑為1nm至10nm。
- 根據申請專利範圍第3項所述的光催化劑,其中,該不連續的塗敷層的厚度為0.1nm至10nm。
- 根據申請專利範圍第1項所述的光催化劑,其中,包含於該多孔性金屬氧化物膜的金屬氧化物包括選自氧化鈦、氧化鎢、氧化鋅、氧化鈮及它們的組合中的至少一種。
- 根據申請專利範圍第1項所述的光催化劑,其中,該金屬粒子包括選自鎢、鉻、釩、鉬、銅、鐵、鈷、錳、鎳、鉑、金、銀、鈰、鎘、鋅、鎂、鈣、鍶、鋇及它們的組合中的至少一種金屬。
- 根據申請專利範圍第1項所述的光催化劑,其中,該多孔性金屬氧化物膜的孔隙度為5%至50%。
- 根據申請專利範圍第1項所述的光催化劑,其中,該多孔性金屬氧化物膜的比表面積為50m2 /g至500m2 /g。
- 根據申請專利範圍第1項所述的光催化劑,其中,每1cm2 該多孔性金屬氧化物膜平面包含0.0001mg至0.01mg的上述金屬粒子。
- 根據申請專利範圍第1項所述的光催化劑,其中,在該光催化劑100wt%中,包含0.01wt%至10wt%的上述金屬粒子。
- 一種光催化劑的製備方法,包括如下步驟:使多孔性金屬氧化物膜成膜的步驟;以及通過濺射法在該多孔性金屬氧化物膜的表面蒸鍍金屬來形成島形狀的不連續的塗敷層的步驟。
- 根據申請專利範圍第12項所述的光催化劑的製備方法,其中,通過利用金屬氧化物前驅體的溶膠-凝膠法,使該多孔性金屬氧化物膜成膜於基板上,或將包含金屬氧化物粉末、粘結劑及溶劑的漿料塗敷於基板來使該多孔性金屬氧化物膜成膜。
- 根據申請專利範圍第12項所述的光催化劑的製備方法,其中,在通過利用金屬氧化物前驅體的溶膠-凝膠法,使該多孔性金屬氧化物膜成膜於基板上後,或者在塗敷包含金屬氧化物粉末、粘結劑及溶劑的漿料來使該多孔性金屬氧化物膜成膜之後,還進行熱處理步驟來形成具有結晶性的該多孔性金屬氧化物膜,或者去除該多孔性金屬氧化物膜內的該粘結劑。
- 根據申請專利範圍第12項所述的光催化劑的製備方法,其中,該濺射法在非活性氣體氛圍下執行。
- 根據申請專利範圍第12項所述的光催化劑的製備方法,其中,該濺射法在3mTorr至10mTorr的壓力條件下執行。
- 根據申請專利範圍第12項所述的光催化劑的製備方法,其中,該濺射法通過施加100W至1000W的電力來執行。
- 一種光催化劑裝置,包括根據申請專利範圍第1項至第11項中任一項所述的光催化劑。
- 根據申請專利範圍第18項所述的光催化劑裝置,其中,適用於空氣淨化、除臭或者抗菌用途。
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