CN104302398A - 光催化剂,该光催化剂的制备方法及光催化剂装置 - Google Patents
光催化剂,该光催化剂的制备方法及光催化剂装置 Download PDFInfo
- Publication number
- CN104302398A CN104302398A CN201280073270.4A CN201280073270A CN104302398A CN 104302398 A CN104302398 A CN 104302398A CN 201280073270 A CN201280073270 A CN 201280073270A CN 104302398 A CN104302398 A CN 104302398A
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- Prior art keywords
- photochemical catalyst
- porous metal
- oxidation film
- metal oxidation
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- Prior art date
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- 239000011941 photocatalyst Substances 0.000 title abstract description 5
- 238000004519 manufacturing process Methods 0.000 title 1
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 22
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 22
- 239000003054 catalyst Substances 0.000 claims description 82
- 229910052751 metal Inorganic materials 0.000 claims description 69
- 239000002184 metal Substances 0.000 claims description 69
- 230000003647 oxidation Effects 0.000 claims description 54
- 238000007254 oxidation reaction Methods 0.000 claims description 54
- 238000004544 sputter deposition Methods 0.000 claims description 18
- 238000002360 preparation method Methods 0.000 claims description 17
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 16
- 229910052709 silver Inorganic materials 0.000 claims description 16
- 239000004332 silver Substances 0.000 claims description 16
- 239000000758 substrate Substances 0.000 claims description 15
- 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
- 230000000694 effects Effects 0.000 claims description 10
- 238000001704 evaporation Methods 0.000 claims description 8
- 230000008020 evaporation Effects 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
- 239000011248 coating agent Substances 0.000 claims description 6
- 238000000576 coating method Methods 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
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 5
- 230000000844 anti-bacterial effect Effects 0.000 claims description 4
- 230000015572 biosynthetic process Effects 0.000 claims description 4
- 230000001877 deodorizing effect Effects 0.000 claims description 4
- 238000000746 purification Methods 0.000 claims description 4
- 239000002002 slurry Substances 0.000 claims description 4
- 238000007581 slurry coating method Methods 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
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 3
- 239000012298 atmosphere Substances 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
- 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
- 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
- 239000002923 metal particle Substances 0.000 abstract 1
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 18
- 230000000052 comparative effect Effects 0.000 description 15
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 9
- 239000000463 material Substances 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 230000005540 biological transmission Effects 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 239000011521 glass Substances 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
- 238000006243 chemical reaction Methods 0.000 description 3
- 230000001699 photocatalysis Effects 0.000 description 3
- 238000002310 reflectometry Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 238000004128 high performance liquid chromatography Methods 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
- 230000031700 light absorption Effects 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- -1 peroxide anion Chemical class 0.000 description 2
- CMPGARWFYBADJI-UHFFFAOYSA-L tungstic acid Chemical compound O[W](O)(=O)=O CMPGARWFYBADJI-UHFFFAOYSA-L 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
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 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
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000006255 coating slurry Substances 0.000 description 1
- 239000012141 concentrate 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
- 239000006185 dispersion Substances 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 108010025899 gelatin film Proteins 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000005259 measurement Methods 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
- 230000006911 nucleation Effects 0.000 description 1
- 238000010899 nucleation Methods 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
- 238000007146 photocatalysis Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000004408 titanium dioxide 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
- 239000011800 void material Substances 0.000 description 1
Classifications
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Abstract
本发明提供一种包括多孔性金属氧化物膜及包含形成于上述多孔性金属氧化物膜的表面的金属粒子的光催化剂。
Description
技术领域
本发明涉及光催化剂,该光催化剂的制备方法及光催化剂装置。
背景技术
二氧化钛(TiO2)作为代表性的光催化物质,是耐久性优秀、耐磨性优秀、安全无毒的物质,具有价格低廉的优点。另一方面,由于带隙能量大,只吸收紫外线以下的光,因而在适用于非外置材料的室内方面存在限度。
基于这种层面,对以用于室内为目的、能够吸收可视光的、对可使可视光具有活性的催化剂进行了很多研究。但是,在许多研究事例中很难找到一贯的倾向,尤其,很难找到在实际居住条件下性能得到验证的结果。
发明内容
本发明要解决的技术问题
本发明的一实例的目的在于,提供一种在室内光源下也具有优秀效率的可视光响应型光催化剂。
本发明的再一实例的目的在于,提供一种制备上述光催化剂的方法。
本发明的另一实例的目的在于,提供一种利用上述光催化剂的光催化剂装置。
技术方案
本发明的一实例提供一种包含多孔性金属氧化物膜及形成于上述多孔性金属氧化物膜的表面的金属粒子的光催化剂。
上述光催化剂对波长在约380nm至约700nm范围的可视光具有活性。
上述金属粒子能够在上述多孔性金属氧化物膜的表面形成岛形状的不连续的涂敷层。
上述岛形状的平均直径可为约1nm至约10nm。
上述不连续的涂敷层的厚度可为约0.1nm至约10nm。
包含在上述多孔性金属氧化物膜的金属氧化物可包含选自氧化钛、氧化钨、氧化锌、氧化铌及它们的组合中的至少一种。
上述金属粒子可包含选自钨、铬、钒、钼、铜、铁、钴、锰、镍、铂、金、银、铈、镉、锌、镁、钙、锶、钡及它们的组合中的至少一种金属。
上述多孔性金属氧化物膜的孔隙度可为约5%至约50%。
上述多孔性金属氧化物膜的比表面积可为约50m2/g至约500m2/g。
每1cm2上述多孔性金属氧化物膜平面包含约0.0001mg至约0.01mg的上述金属粒子。
在上述光催化剂100wt%中,可包含0.01wt%至10wt%含量的上述金属粒子。
本发明的再一实例提供一种光催化剂的制备方法,其特征在于,包括如下步骤:使多孔性金属氧化物膜成膜的步骤;以及通过溅射法在上述多孔性金属氧化物膜的表面蒸镀金属来形成岛形状的不连续的涂敷层的步骤。
根据利用金属氧化物前驱体的溶胶-凝胶法,使上述多孔性金属氧化物膜成膜于基板上,或者可将包含金属氧化物粉末、粘结剂及溶剂的浆料涂敷于基板来使上述多孔性金属氧化物膜成膜。
在根据利用金属氧化物前驱体的溶胶-凝胶法,使上述多孔性金属氧化物膜成膜于基板上后,或者在涂敷包含金属氧化物粉末、粘结剂及溶剂的浆料来使上述多孔性金属氧化物膜成膜之后,还可进行热处理步骤来形成具有结晶性的上述多孔性金属氧化物膜,或者可去除上述多孔性金属氧化物膜内的上述粘结剂。
上述溅射法可在非活性气体氛围下执行。
上述溅射法可在约3mTorr至约10mTorr的压力条件下执行。
上述溅射法可通过施加约100W至约1000W的电力来执行。
本发明的另一实例提供一种包括上述光催化剂的光催化剂装置。
上述光催化剂装置可适用于空气净化、除臭或者抗菌用途上。
有益效果
上述光催化剂对可见光进行响应,并具有优秀的光催化效率。
附图说明
图1是在实施例1中制备的光催化剂的金属粒子的涂敷层侧表面的30000倍率透射电子显微镜(TEM)的图像。
图2是在实施例1中制备的光催化剂的金属粒子的涂敷层侧表面的100000倍率透射电子显微镜(TEM)的图像。
图3是表示对上述实施例1至实施例2及比较例1至比较例2的光催化剂的紫外线吸收率及可见光的吸收率的曲线图。
具体实施方式
以下,对本发明的实例进行详细说明。但,这只是例示性的,本发明不被此所限制,本发明仅根据所附的发明要求保护范围来定义。
本发明的一实例提供一种包含多孔性金属氧化物膜及形成于上述多孔性金属氧化物膜的表面的金属粒子的光催化剂。形成上述多孔性金属氧化物膜的金属氧化物可不受限制地使用作为光催化剂使用的作为金属氧化物所公知的物质。上述金属粒子的金属可使用掺杂于上述金属氧化物来能够赋予上述光催化剂对可见光的活性的种类的金属。上述金属粒子的金属,例如,可以是过渡金属、贵金属等。
上述光催化剂可对波长在约380nm至约700nm范围的可见光具有活性。可见光吸收率可通过对100%的全部光除于透射率与反射率的值来计算,并且,根据这种计算方式,本发明的光催化剂,具体地,能够以约2%至约20%的吸收率吸收波长在约380nm以上至约700nm以下范围的可见光。
上述光催化剂是一种从吸收光而得到的能量中生成的电子与空穴生成过氧化物负离子或者羟自由基等,来能够起到空气净化、除臭、抗菌作用的物质。例如,从上述光催化剂生成的过氧化物负离子或者羟自由基能够分解如甲醛等的有害环境物质。另一方面,由于上述光催化剂对可见光具有吸收率,在室内光源下也表现出优秀的效率,因而可不需要额外的紫外线供给装置。
上述金属粒子可在上述多孔性金属氧化物膜的表面形成岛形状的不连续的涂敷层。上述岛形状的平均直径可为约1nm至约10nm,具体地,平均直径可为约3nm至约8nm。上述金属粒子的不连续的涂敷层可根据溅射法蒸镀金属来形成。通过使上述岛形状的直径如同上述范围形成小的微粒,能够更加提高上述光催化剂对可见光的活性效率。因此,优选地,上述金属粒子为根据溅射法来蒸镀的微粒,能够形成上述不连续的涂敷层。并且,由于通过溅射法形成上述金属粒子的不连续的涂敷层,因而各岛形状或者金属粒子的微粒的粒径分布能够稳定。由于像这样蒸镀形成具有分散度低的粒径分布的金属粒子的微粒,因而上述不连续的涂敷层的各岛形状的直径分布的分散度也低。例如,上述岛形状的直径的D50可具有约5nm以下的值,D90可具有约10nm以下的值。在具有上述范围的分布度的情况下,上述光催化剂对可见光的活性效率能够更加优秀。
如此地,上述光催化剂为了赋予对可见光的活性,为了将上述金属掺杂于上述金属氧化物,根据溅射法将上述金属涂敷于上述多孔性金属氧化物膜的表面,使得上述金属粒子形成于多孔性金属氧化物膜表面。这时,如上所述,可根据溅射法使上述金属粒子均匀地分布在多孔性金属氧化物膜的表面。此时,如上所述,可以通过溅射法分布成使上述金属粒子均匀地分散在多孔性金属氧化物膜的表面。例如,每1cm2上述多孔性金属氧化物膜平面包含约0.0001mg至约0.01mg的上述金属粒子,具体地,每1cm2上述多孔性金属氧化物膜平面包含约0.001mg至约0.005mg上述金属粒子。由上述范围的含量比均匀掺杂上述金属的上述光催化剂对可见光的活性效率能够更加优秀。
上述金属粒子的上述不连续的涂敷层的厚度可为约0.1nm至约10nm。上述金属粒子的上述不连续的涂敷层的厚度小于上述厚度范围时,很难期待可见光活性,而大于上述厚度范围时,由于形成连续的膜,因此具有不能顺利进行光吸收的问题。
例如,在100wt%的上述光催化剂中,可包含约0.01wt%至约10wt%含量的上述金属粒子。上述金属粒子的含量小于上述范围时,很难期待基于添加金属粒子的效果,而大于上述范围时,可能会起到作为金属氧化物光催化剂而抑制光吸收的要素的作用。
上述金属可包括选自钨、铬、钒、钼、铜、铁、钴、锰、镍、铂、金、银、铈、镉、锌、镁、钙、锶、钡及它们的组合中的至少一种。
包含在上述多孔性金属氧化物膜的金属氧化物可包括选自氧化钛、氧化钨、氧化锌、氧化铌及它们的组合中的至少一种。
上述多孔性金属氧化物膜的孔隙度可为约5%至约50%。如果上述多孔性金属氧化物膜具有上述范围的孔隙度,则上述光催化剂对可见光的活性效率能够更加优秀。如果,多孔性金属氧化物膜根据溅射方法等,周密地形成而不具有孔隙,则很难有效地吸附甲醛等反应物,导致难以期待优秀的光催化活性。
上述多孔性金属氧化物膜的比表面积可为约50m2/g至约500m2/g。如果上述多孔性金属氧化物膜具有上述范围的比表面积,则上述光催化剂对可见光的活性效率能够更加优秀。
在本发明的另一实例,提供一种光催化剂的制备方法,其包括如下步骤:使多孔性金属氧化物膜成膜的步骤;以及通过溅射法在上述多孔性金属氧化物膜的表面蒸镀金属来在上述多孔性金属氧化物膜的表面形成岛形状的不连续的涂敷层的步骤。
可根据上述光催化剂的制备方法来制备出如上所述的光催化剂。
为了使上述多孔性金属氧化物膜成膜,例如,可利用溶剂法在基板上形成上述多孔性金属氧化物膜。并且,例如,上述基板可使用玻璃基板。
在一实例中,可根据利用金属氧化物的前驱体的溶胶-凝胶法,使上述多孔性金属氧化物膜成膜于基板上。具体地,可在以溶胶形态涂敷包含金属氧化物前驱体的溶剂之后,进行干燥以凝胶状成膜,之后执行热处理步骤来形成具有结晶性的膜。例如,准备如金属醇盐等的包含上述金属氧化物前驱体、乙醇、酸等的溶液后进行水解,并且通过脱水、脱乙醇得到溶胶状态后,就能够涂敷于平板型基板。上述溶胶-凝胶法可根据公知的工序条件来执行,不受特定条件的限制。
在再一实例中,首先,可通过将包含金属氧化物粉末、粘结剂及溶剂的浆料涂敷于基板上来成膜。根据这种浆料涂敷法来形成多孔性金属氧化物膜的具体的工序条件也可根据公知条件来执行,不受特定条件的限制。上述粘结剂是用于将金属氧化物固定于基板上的,例如,可将树脂用作粘结剂来使用,且可在基板上涂敷浆料后进行热处理来去除上述粘结剂。
具体地,上述溅射法可在氩等的非活性气体氛围下,以及约1mTorr至约10mTorr的工序压力条件下,施加200W至1000W的电力来执行数秒钟至数分钟。
上述光催化剂的制备方法由于根据溅射法蒸镀上述金属来在上述多孔性金属氧化物膜形成不连续的涂敷层,因而上述光催化剂的制备方法具有能够对大面积基板均匀地涂敷的利点,并且能够使上述金属粒子以纳米大小均匀分散来形成涂敷层。根据这种光催化剂的制备方法制备的光催化剂,能够更加提高对可见光的活性。
在本发明的另一实例中,提供一种包含上述光催化剂的光催化剂装置。上述光催化剂装置,例如,可制备成空气净化、除臭、抗菌用途的装置。
以下,记载本发明的实施例以及比较例。但是,这种下述的实施例只是本发明的一实施例,而本发明并不限定于下述的实施例。
实施例
实施例1
作为二氧化钛(TiO2),使用了德固萨(Degussa)的P25。将P25分散于异丙醇,制备出浓度为5wt%的P25异丙醇浆料。用均质器(Homogenizer)对上述浆料进行30分钟处理后,得到了均匀分散液。将此分散液涂敷于不含Na(Na-free)的0.7t的玻璃。使涂敷量以P25基准成为1g/m2。对涂敷有上述二氧化钛(TiO2)的玻璃进行溅射来形成了不连续的岛形状的银(Ag)涂敷层。作为靶使用了银(Ag)金属,工序压力为3mTorr、直流(DC)电力为500W,并且作为非活性气体注入了100cc/min的氩气,蒸镀了5秒钟。以上述方法制备了银(Ag)/二氧化钛(TiO2)光催化剂。所制备的光催化剂的金属氧化物的孔隙度为约20%、比表面积为约56m2/g,并且银(Ag)金属粒子中的光催化剂的含量为0.6wt%,每平面的多孔性金属氧化物(TiO2)膜的银(Ag)金属粒子含量为0.0026mg/cm2。根据TEM(JEOL,JEM-2010)测定的结果,上述岛形状的银(Ag)涂敷层的厚度为1nm。
实施例2
除了使用三氧化钨(WO3)粉末(Aldrich)来代替二氧化钛(TiO2)之外,以与实施例1相同的方法制备出Ag/WO3光催化剂。所制备的光催化剂的金属氧化物的孔隙度为约20%、比表面积为约52m2/g,并且光催化剂中的银(Ag)金属粒子的含量为0.4wt%、每平面的多孔性金属氧化物(WO3)膜的银(Ag)金属粒子的含量为0.0026mg/cm2。根据TEM(JEOL,JEM-2010)测定的结果,上述岛形状的银(Ag)涂敷层的厚度为1nm。
比较例1
在实施例1中不形成银(Ag)涂敷层来制备出二氧化钛(TiO2)多孔性膜来制备了光催化剂。
比较例2
实施例2中不形成银(Ag)涂敷层来制备出三氧化钨(WO3)多孔性膜来制备了光催化剂。
比较例3
在第一反应器中放入四异丙醇钛142g、异丙醇72g和二乙酰基甲烷10g,并在常温下进行了30分钟的反应。在第二反应器中放入蒸馏水760g、硝酸铁1.4g、硝酸锌2.6g、硝酸铜1.8g后以400rpm进行搅拌,使金属盐完全溶解。慢慢向上述第二反应器投入上述第一反应器的溶液后滴下(dropping)1.6g的硝酸,再将温度升温至80℃后,进行了3小时的反应。最后,投入7.6g的正硅酸三乙酯(triethylorthosilicate),进行了1小时的反应,制备出透明的可见光活性二氧化钛类光催化剂。
图1是在上述实施例1中制备的光催化剂的银(Ag)涂敷层侧表面的30000倍率透射电子显微镜(TEM)图像,图2是在实施例1中制备的光催化剂的银(Ag)涂敷层侧表面的100000倍率透射电子显微镜(TEM)图像。通过图1及图2能够确认形成于多孔性金属氧化物表面的金属粒子的平均直径大小为约5nm。
实验例1
对实施例1至实施例2及比较例1至比较例2中制备的光催化剂,评价了基于波长的紫外线吸收率及可见光吸收率。在300nm至780nm的波长范围内进行了测量,以对100%的全部光除于透射率与反射率的值作为吸收率来进行了计算。
图3图示出根据利用岛津(Shimadzu)公司的Solidspec-3700型号,由上述实施例1至实施例2及比较例1至比较例2的光催化剂的透射率与反射率的测量结果计算出紫外线的吸收率及可见光的吸收率的结果。
实验例2
对实施例1及比较例3的光催化剂评价了去除甲醛的性能。将在实施例1及比较例3中制备的涂敷有光催化剂的玻璃(165mm×165mm×0.7mm)设置在20L的小型腔体(ADTEC社:进达科贸易(深圳)有限公司产品)内,然后以167cc/min的流量持续向腔体内流入甲醛浓度为0.08ppm的净化空气,且使换气次数达到0.5次/hr。作为光源使用了10W的白色荧光灯,且将照度设成1000勒克斯(lux)。测量净化空气进入腔体之前的浓度与通过腔体后的浓度来计算了甲醛去除率,并记录到下表1。利用2,4-二硝基苯肼(DNPH,2,4-dinitrophenylhydrazine)暗盒浓缩相对于10L的量,再利用高性能高效液相色谱法(HPLC,Agilent安捷伦公司产品)分析了浓度。
表1
区分 | 甲醛去除率 |
实施例1 | 81% |
实施例2 | 85% |
比较例1 | 0 |
比较例2 | 0 |
比较例3 | 0% |
Claims (19)
1.一种光催化剂,其特征在于,包括:
多孔性金属氧化物膜;以及
金属粒子,其形成于所述多孔性金属氧化物膜的表面。
2.根据权利要求1所述的光催化剂,其特征在于,对波长在380nm至700nm范围内的可见光具有活性。
3.根据权利要求1所述的光催化剂,其特征在于,所述金属粒子在所述多孔性金属氧化物膜的表面形成岛形状的不连续的涂敷层。
4.根据权利要求3所述的光催化剂,其特征在于,所述岛形状的平均直径为1nm至10nm。
5.根据权利要求3所述的光催化剂,其特征在于,所述不连续的涂敷层的厚度为0.1nm至10nm。
6.根据权利要求1所述的光催化剂,其特征在于,包含于所述多孔性金属氧化物膜的金属氧化物包括选自氧化钛、氧化钨、氧化锌、氧化铌及它们的组合中的至少一种。
7.根据权利要求1所述的光催化剂,其特征在于,所述金属粒子包括选自钨、铬、钒、钼、铜、铁、钴、锰、镍、铂、金、银、铈、镉、锌、镁、钙、锶、钡及它们的组合中的至少一种金属。
8.根据权利要求1所述的光催化剂,其特征在于,所述多孔性金属氧化物膜的孔隙度为5%至50%。
9.根据权利要求1所述的光催化剂,其特征在于,所述多孔性金属氧化物膜的比表面积为50m2/g至500m2/g。
10.根据权利要求1所述的光催化剂,其特征在于,每1cm2所述多孔性金属氧化物膜平面包含0.0001mg至0.01mg的所述金属粒子。
11.根据权利要求1所述的光催化剂,其特征在于,在所述光催化剂100wt%中,包含0.01wt%至10wt%的所述金属粒子。
12.一种光催化剂的制备方法,其特征在于,包括如下步骤:
使多孔性金属氧化物膜成膜的步骤;以及
通过溅射法在所述多孔性金属氧化物膜的表面蒸镀金属来形成岛形状的不连续的涂敷层的步骤。
13.根据权利要求12所述的光催化剂的制备方法,其特征在于,通过利用金属氧化物前驱体的溶胶-凝胶法,使所述多孔性金属氧化物膜成膜于基板上,或者将包含金属氧化物粉末、粘结剂及溶剂的浆料涂敷于基板来使所述多孔性金属氧化物膜成膜。
14.根据权利要求12所述的光催化剂的制备方法,其特征在于,在通过利用金属氧化物前驱体的溶胶-凝胶法,使所述多孔性金属氧化物膜成膜于基板上后,或者在涂敷包含金属氧化物粉末、粘结剂及溶剂的浆料来使所述多孔性金属氧化物膜成膜之后,还进行热处理步骤来形成具有结晶性的所述多孔性金属氧化物膜,或者去除所述多孔性金属氧化物膜内的所述粘结剂。
15.根据权利要求12所述的光催化剂的制备方法,其特征在于,所述溅射法在非活性气体氛围下执行。
16.根据权利要求12所述的光催化剂的制备方法,其特征在于,所述溅射法在3mTorr至10mTorr的压力条件下执行。
17.根据权利要求12所述的光催化剂的制备方法,其特征在于,所述溅射法通过施加100W至1000W的电力来执行。
18.一种光催化剂装置,其特征在于,包括根据权利要求1至11中任一项所述的光催化剂。
19.根据权利要求18所述的光催化剂装置,其特征在于,适用于空气净化、除臭或者抗菌用途。
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