JP2007075678A - Zirconium oxide-based optically functional oxide - Google Patents
Zirconium oxide-based optically functional oxide Download PDFInfo
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- JP2007075678A JP2007075678A JP2005263580A JP2005263580A JP2007075678A JP 2007075678 A JP2007075678 A JP 2007075678A JP 2005263580 A JP2005263580 A JP 2005263580A JP 2005263580 A JP2005263580 A JP 2005263580A JP 2007075678 A JP2007075678 A JP 2007075678A
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- oxide
- photofunctional
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- visible light
- photocatalyst
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- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 title claims abstract description 33
- 229910001928 zirconium oxide Inorganic materials 0.000 title claims abstract description 33
- 239000011941 photocatalyst Substances 0.000 claims abstract description 43
- 229910052751 metal Inorganic materials 0.000 claims abstract description 27
- 230000001699 photocatalysis Effects 0.000 claims abstract description 27
- 229910052715 tantalum Inorganic materials 0.000 claims abstract description 14
- 229910052742 iron Inorganic materials 0.000 claims abstract description 13
- 229910052758 niobium Inorganic materials 0.000 claims abstract description 13
- 229910052787 antimony Inorganic materials 0.000 claims abstract description 12
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 12
- 238000004519 manufacturing process Methods 0.000 claims abstract description 10
- 239000002184 metal Substances 0.000 claims description 25
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 24
- 239000002994 raw material Substances 0.000 claims description 22
- 239000010955 niobium Substances 0.000 claims description 20
- 239000011651 chromium Substances 0.000 claims description 16
- 150000002736 metal compounds Chemical class 0.000 claims description 14
- 239000000047 product Substances 0.000 claims description 13
- 239000003513 alkali Substances 0.000 claims description 8
- 239000002244 precipitate Substances 0.000 claims description 8
- 206010034960 Photophobia Diseases 0.000 claims description 7
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 7
- 208000013469 light sensitivity Diseases 0.000 claims description 7
- 229910052726 zirconium Inorganic materials 0.000 claims description 7
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 claims description 6
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims description 5
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims description 5
- 230000003287 optical effect Effects 0.000 claims description 5
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 4
- 238000001354 calcination Methods 0.000 claims description 4
- 239000007795 chemical reaction product Substances 0.000 claims description 4
- 239000000470 constituent Substances 0.000 claims description 3
- 238000006243 chemical reaction Methods 0.000 abstract description 8
- 238000000034 method Methods 0.000 abstract description 8
- 238000001556 precipitation Methods 0.000 abstract description 6
- 229910000765 intermetallic Inorganic materials 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 33
- 239000000843 powder Substances 0.000 description 18
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 17
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 12
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 10
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 9
- 239000000203 mixture Substances 0.000 description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 6
- 239000001257 hydrogen Substances 0.000 description 6
- 229910052739 hydrogen Inorganic materials 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- CXKWCBBOMKCUKX-UHFFFAOYSA-M methylene blue Chemical compound [Cl-].C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 CXKWCBBOMKCUKX-UHFFFAOYSA-M 0.000 description 6
- 229960000907 methylthioninium chloride Drugs 0.000 description 6
- CMOAHYOGLLEOGO-UHFFFAOYSA-N oxozirconium;dihydrochloride Chemical compound Cl.Cl.[Zr]=O CMOAHYOGLLEOGO-UHFFFAOYSA-N 0.000 description 6
- 238000007254 oxidation reaction Methods 0.000 description 5
- 238000006722 reduction reaction Methods 0.000 description 5
- OEIMLTQPLAGXMX-UHFFFAOYSA-I tantalum(v) chloride Chemical compound Cl[Ta](Cl)(Cl)(Cl)Cl OEIMLTQPLAGXMX-UHFFFAOYSA-I 0.000 description 5
- 239000011787 zinc oxide Substances 0.000 description 5
- 229910021555 Chromium Chloride Inorganic materials 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 4
- VZJJZMXEQNFTLL-UHFFFAOYSA-N chloro hypochlorite;zirconium;octahydrate Chemical compound O.O.O.O.O.O.O.O.[Zr].ClOCl VZJJZMXEQNFTLL-UHFFFAOYSA-N 0.000 description 4
- QSWDMMVNRMROPK-UHFFFAOYSA-K chromium(3+) trichloride Chemical compound [Cl-].[Cl-].[Cl-].[Cr+3] QSWDMMVNRMROPK-UHFFFAOYSA-K 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 230000031700 light absorption Effects 0.000 description 4
- 150000004689 octahydrates Chemical class 0.000 description 4
- YHBDIEWMOMLKOO-UHFFFAOYSA-I pentachloroniobium Chemical compound Cl[Nb](Cl)(Cl)(Cl)Cl YHBDIEWMOMLKOO-UHFFFAOYSA-I 0.000 description 4
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 description 4
- -1 superoxide ions Chemical class 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 229910010413 TiO 2 Inorganic materials 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
- LJAOOBNHPFKCDR-UHFFFAOYSA-K chromium(3+) trichloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].[Cl-].[Cl-].[Cr+3] LJAOOBNHPFKCDR-UHFFFAOYSA-K 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000011630 iodine Substances 0.000 description 3
- 229910052740 iodine Inorganic materials 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 230000003595 spectral effect Effects 0.000 description 3
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 2
- 239000005751 Copper oxide Substances 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- FAPDDOBMIUGHIN-UHFFFAOYSA-K antimony trichloride Chemical compound Cl[Sb](Cl)Cl FAPDDOBMIUGHIN-UHFFFAOYSA-K 0.000 description 2
- 239000001045 blue dye Substances 0.000 description 2
- KJKIXUGJRPCYTP-UHFFFAOYSA-N chromium hexahydrate Chemical compound O.O.O.O.O.O.[Cr] KJKIXUGJRPCYTP-UHFFFAOYSA-N 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 229910000431 copper oxide Inorganic materials 0.000 description 2
- 238000004042 decolorization Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 2
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 description 2
- IZEMHEXSGIOXDA-UHFFFAOYSA-N iron;hexahydrate Chemical compound O.O.O.O.O.O.[Fe] IZEMHEXSGIOXDA-UHFFFAOYSA-N 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 239000004570 mortar (masonry) Substances 0.000 description 2
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- 239000006228 supernatant Substances 0.000 description 2
- 229910001930 tungsten oxide Inorganic materials 0.000 description 2
- OERNJTNJEZOPIA-UHFFFAOYSA-N zirconium nitrate Chemical compound [Zr+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O OERNJTNJEZOPIA-UHFFFAOYSA-N 0.000 description 2
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 229910002367 SrTiO Inorganic materials 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 1
- XHCLAFWTIXFWPH-UHFFFAOYSA-N [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] Chemical group [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] XHCLAFWTIXFWPH-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000004703 alkoxides Chemical class 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 235000012501 ammonium carbonate Nutrition 0.000 description 1
- 239000001099 ammonium carbonate Substances 0.000 description 1
- 229910000410 antimony oxide Inorganic materials 0.000 description 1
- VMPVEPPRYRXYNP-UHFFFAOYSA-I antimony(5+);pentachloride Chemical compound Cl[Sb](Cl)(Cl)(Cl)Cl VMPVEPPRYRXYNP-UHFFFAOYSA-I 0.000 description 1
- 239000003125 aqueous solvent Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- CXKCTMHTOKXKQT-UHFFFAOYSA-N cadmium oxide Inorganic materials [Cd]=O CXKCTMHTOKXKQT-UHFFFAOYSA-N 0.000 description 1
- CFEAAQFZALKQPA-UHFFFAOYSA-N cadmium(2+);oxygen(2-) Chemical compound [O-2].[Cd+2] CFEAAQFZALKQPA-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 229940068911 chloride hexahydrate Drugs 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 150000001844 chromium Chemical class 0.000 description 1
- 229910000423 chromium oxide Inorganic materials 0.000 description 1
- 229910000428 cobalt oxide Inorganic materials 0.000 description 1
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 1
- CEJANLKHJMMNQB-UHFFFAOYSA-M cryptocyanin Chemical compound [I-].C12=CC=CC=C2N(CC)C=CC1=CC=CC1=CC=[N+](CC)C2=CC=CC=C12 CEJANLKHJMMNQB-UHFFFAOYSA-M 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 150000004687 hexahydrates Chemical class 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 229910003437 indium oxide Inorganic materials 0.000 description 1
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 description 1
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical class Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 description 1
- SURQXAFEQWPFPV-UHFFFAOYSA-L iron(2+) sulfate heptahydrate Chemical compound O.O.O.O.O.O.O.[Fe+2].[O-]S([O-])(=O)=O SURQXAFEQWPFPV-UHFFFAOYSA-L 0.000 description 1
- WOSISLOTWLGNKT-UHFFFAOYSA-L iron(2+);dichloride;hexahydrate Chemical compound O.O.O.O.O.O.Cl[Fe]Cl WOSISLOTWLGNKT-UHFFFAOYSA-L 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 150000004692 metal hydroxides Chemical class 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 229910000480 nickel oxide Inorganic materials 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- UJVRJBAUJYZFIX-UHFFFAOYSA-N nitric acid;oxozirconium Chemical compound [Zr]=O.O[N+]([O-])=O.O[N+]([O-])=O UJVRJBAUJYZFIX-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000006053 organic reaction Methods 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- VTRUBDSFZJNXHI-UHFFFAOYSA-N oxoantimony Chemical compound [Sb]=O VTRUBDSFZJNXHI-UHFFFAOYSA-N 0.000 description 1
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical group [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- BPUBBGLMJRNUCC-UHFFFAOYSA-N oxygen(2-);tantalum(5+) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Ta+5].[Ta+5] BPUBBGLMJRNUCC-UHFFFAOYSA-N 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 239000003504 photosensitizing agent Substances 0.000 description 1
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical compound N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 description 1
- OGHBATFHNDZKSO-UHFFFAOYSA-N propan-2-olate Chemical compound CC(C)[O-] OGHBATFHNDZKSO-UHFFFAOYSA-N 0.000 description 1
- 230000002468 redox effect Effects 0.000 description 1
- 229910001925 ruthenium oxide Inorganic materials 0.000 description 1
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(iv) oxide Chemical compound O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 229910001936 tantalum oxide Inorganic materials 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 229910001935 vanadium oxide Inorganic materials 0.000 description 1
- ZXAUZSQITFJWPS-UHFFFAOYSA-J zirconium(4+);disulfate Chemical compound [Zr+4].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O ZXAUZSQITFJWPS-UHFFFAOYSA-J 0.000 description 1
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- Catalysts (AREA)
Abstract
Description
本発明は、光触媒作用を有するジルコニウム含有結晶性金属化合物であって、従来の酸化チタン光触媒とは異なる組成を有する新しい酸化ジルコニウム系光機能性酸化物に関するものであり、更に詳しくは、本発明は、一般式：（ＺｒＯ２）１−ｎ［（Ｍ１Ｏ５／２）（Ｍ２Ｏ３／２）］ｎ（式中、Ｍ１はＮｂ、Ｔａ、Ｓｂから選ばれる少なくとも一種の金属元素、Ｍ２はＣｒ、Ｆｅから選ばれる少なくとも一種の金属元素を表す。）で表される組成の可視光感受性を有する酸化ジルコニウム系光機能性酸化物に関するものである。本発明は、光触媒の技術分野において、可視光感受性を利用した新しい光触媒として、現在広く使われている光触媒である酸化チタンの利用分野等への適用に限らず、幅広く、脱臭、殺菌、排水処理、有機反応等への利用を可能にする新しい酸化ジルコニウム系光機能性酸化物及び光触媒製品に関する新技術・新製品を提供することを実現するものである。 The present invention relates to a zirconium-containing crystalline metal compound having a photocatalytic action, and relates to a new zirconium oxide-based photofunctional oxide having a composition different from that of the conventional titanium oxide photocatalyst. , General formula: (ZrO 2 ) 1-n [(M 1 O 5/2 ) (M 2 O 3/2 )] n (wherein M 1 is at least one metal element selected from Nb, Ta, and Sb) , M 2 represents at least one metal element selected from Cr and Fe.) And relates to a zirconium oxide photofunctional oxide having a visible light sensitivity and a composition represented by: In the technical field of photocatalysts, as a new photocatalyst using visible light sensitivity, the present invention is not limited to the application field of titanium oxide, which is a photocatalyst that is currently widely used. It is intended to provide new technologies and new products related to new zirconium oxide-based photofunctional oxides and photocatalytic products that can be used for organic reactions and the like.
従来、光機能性酸化物として、例えば、酸化チタン、酸化亜鉛、酸化ジルコニウム、酸化アンチモン等が知られているが、その中で光触媒として最も広く使われている酸化チタンは、４００ｎｍ以下の波長の紫外光によってのみ励起されて光触媒特性を発現する。酸化チタンは、波長４００ｎｍ以下の光に照射されると、励起されて電子が導電帯に移動し、移動した電子の跡には正孔ができる。光触媒である酸化チタンに生じた電子と正孔は、その粒子の表面に移動して、電子による還元反応と正孔による酸化反応が生じる。 Conventionally, as photofunctional oxides, for example, titanium oxide, zinc oxide, zirconium oxide, antimony oxide, and the like are known. Among them, titanium oxide that is most widely used as a photocatalyst has a wavelength of 400 nm or less. Excited only by ultraviolet light to develop photocatalytic properties. When titanium oxide is irradiated with light having a wavelength of 400 nm or less, it is excited and electrons move to the conduction band, and holes are formed in the traces of the moved electrons. Electrons and holes generated in titanium oxide as a photocatalyst move to the surface of the particle, and a reduction reaction by electrons and an oxidation reaction by holes occur.
表面に移動した電子は、酸化チタン表面に存在する酸素を還元してＯ２ −（スーパーオキシドイオン）を生成し、それが水分と反応して、過酸化水素を経て、更にＯＨ・ラジカルが生成すると云われている。このＯＨ・ラジカルは、オゾンより強い酸化力を示し、あらゆる有機物のチェーンを切断したり、これを酸化・分解反応により炭素や水に変化させる。正孔は、結晶表面の水分やＯＨ基と反応してＯＨ・（ヒドロキシラジカル）を生成し、このＯＨ・ラジカルが酸化反応に係わると云われている。このような酸化チタンによる酸化還元作用は、太陽光エネルギー全体の約５％以下しか含まれない紫外光によってのみ生じるものである。従って、酸化チタンは、太陽光の利用効率が極めて低く、また、紫外光のないところでは利用することができない。 Moved electrons on the surface, by reducing oxygen present in the surface of titanium oxide with the O 2 - generate (superoxide ions), it reacts with water, through the hydrogen peroxide, further OH · radicals generated It is said that. This OH · radical has a stronger oxidizing power than ozone and breaks any organic chain or changes it to carbon or water by oxidation / decomposition reaction. It is said that the holes react with moisture and OH groups on the crystal surface to generate OH · (hydroxy radical), and this OH · radical is involved in the oxidation reaction. Such an oxidation-reduction effect by titanium oxide is caused only by ultraviolet light that is contained by about 5% or less of the total solar energy. Therefore, titanium oxide has very low utilization efficiency of sunlight and cannot be used in the absence of ultraviolet light.
従来、可視光による光触媒作用を有する光触媒を開発するために、多くの提案がなされてきた。先行技術として、例えば、（１）熱分解法により得られ、窒素を含み、一般式：ＭＯｘ−ＴｉＯ２（ＭＯｘは、酸化ニッケル、酸化コバルト、酸化タングステン、酸化亜鉛、酸化鉄、酸化銅、酸化タンタル、酸化ジルコニウム）で表される、チタン以外の金属酸化物と酸化チタンよりなる可視光感受性を有する複合光触媒（特許文献１参照）、（２）アナターゼ型酸化チタンを基材とし、この表面に酸化鉄（ＦｅＯ、Ｆｅ２Ｏ３、Ｆｅ３Ｏ４、ＦｅＴｉＯ３等）を有し、かつＢＥＴ比表面積が５５ｍ２／ｇ以上である光触媒体（特許文献２参照）、（３）光触媒作用を有する酸化チタンに、金属フタロシアニン、クリプトシアニン等の光増感剤を付着させて室内でも光触媒作用を達成する方法（特許文献３参照）、等が報告されている。 Conventionally, many proposals have been made to develop a photocatalyst having a photocatalytic action by visible light. As a prior art, for example, (1) obtained by a thermal decomposition method and containing nitrogen, the general formula: MOx-TiO 2 (MOx is nickel oxide, cobalt oxide, tungsten oxide, zinc oxide, iron oxide, copper oxide, oxidation A composite photocatalyst having a visible light sensitivity composed of a metal oxide other than titanium and titanium oxide (refer to Patent Document 1) represented by (tantalum, zirconium oxide), and (2) an anatase-type titanium oxide as a base material. A photocatalyst having iron oxide (FeO, Fe 2 O 3 , Fe 3 O 4 , FeTiO 3, etc.) and having a BET specific surface area of 55 m 2 / g or more (see Patent Document 2), (3) Photocatalytic action A method for achieving a photocatalytic action indoors by attaching a photosensitizer such as metal phthalocyanine or cryptocyanine to titanium oxide (see Patent Document 3) has been reported. The
また、酸化チタン光触媒以外の光触媒に関しては、例えば、酸化亜鉛光触媒は、酸化チタン光触媒と同様に、波長が短い紫外光しか吸収しないため、可視光による光触媒反応は殆ど起こらないが、これを可視光感受性にするために、例えば、（４）一般式：ＭＯｘ−ＺｎＯ（ＭＯｘは、酸化バナジウム、酸化鉄、酸化タングステン、酸化銅、酸化タンタル、酸化ルテニウム、酸化クロム、酸化マンガン、酸化カドニウム、酸化インジウム等の可視光を吸収できる金属酸化物）からなる可視光感受性の酸化亜鉛光触媒（特許文献４参照）、が提案されている。 As for photocatalysts other than the titanium oxide photocatalyst, for example, the zinc oxide photocatalyst absorbs only ultraviolet light having a short wavelength as in the case of the titanium oxide photocatalyst. In order to make it sensitive, for example, (4) General formula: MOx-ZnO (MOx is vanadium oxide, iron oxide, tungsten oxide, copper oxide, tantalum oxide, ruthenium oxide, chromium oxide, manganese oxide, cadmium oxide, indium oxide. A visible light sensitive zinc oxide photocatalyst (refer to Patent Document 4) made of a metal oxide capable of absorbing visible light, etc.) has been proposed.
また、酸化ジルコニウムは、光触媒としての特性を有し、紫外光照射により触媒作用を発揮することが知られているが、この酸化ジルコニウム光触媒を作製する方法として、例えば、（５）硫酸ジルコニウムをメタノール等の有機溶媒に溶解・反応して得られるゾルゲル反応により得たゲルを、常温で乾燥するだけの簡便な方法で酸化ジルコニウム光触媒を得る方法（特許文献５参照）、また、（６）ジルコン酸イソプロポキシドを粒状活性アルミナに担持して焼成する酸化ジルコニウム光触媒の担持方法（特許文献６参照）、等が提案されている。 Zirconium oxide has characteristics as a photocatalyst and is known to exhibit a catalytic action when irradiated with ultraviolet light. As a method for producing this zirconium oxide photocatalyst, for example, (5) zirconium sulfate is converted to methanol. A method of obtaining a zirconium oxide photocatalyst by a simple method in which a gel obtained by dissolving and reacting in an organic solvent such as sol-gel reaction is dried at room temperature (see Patent Document 5), and (6) zirconic acid A method of supporting a zirconium oxide photocatalyst in which isopropoxide is supported on granular activated alumina and calcined (see Patent Document 6) has been proposed.
酸化ジルコニウム光触媒は、紫外光にのみ感受性を示して酸化還元作用を発現するが、可視光には感受性を有しないため、太陽光の利用効率が悪いという欠点がある。これは、酸化ジルコニウムのバンドギャップが約５．０ｅ．Ｖと大きいため、太陽光の中の紫外光だけにしか反応せず、太陽光エネルギーの大半を占める可視光をほとんど吸収しないからである。従って、この光触媒は、紫外光のないところでは使用できないことになり、その応用範囲が限定される。例えば、可視光で反応する光触媒であれば、普通の安価なガラス容器等が使えるが、紫外光応答型の光触媒では、紫外光を吸収しない容器、例えば、石英ガラス容器等を特別に細工して使用しなければならないため、高価な装置になる。また、装置にも紫外光発生器を余分に装備しなければならないという問題がある。 Zirconium oxide photocatalysts are sensitive only to ultraviolet light and exhibit a redox effect, but have no drawback to the efficiency of sunlight utilization because they are not sensitive to visible light. This is because the band gap of zirconium oxide is about 5.0 e. This is because V is so large that it reacts only to ultraviolet light in sunlight and hardly absorbs visible light that occupies most of the solar energy. Therefore, this photocatalyst cannot be used in the absence of ultraviolet light, and its application range is limited. For example, if it is a photocatalyst that reacts with visible light, an ordinary inexpensive glass container can be used. However, with an ultraviolet light-responsive photocatalyst, a container that does not absorb ultraviolet light, such as a quartz glass container, is specially crafted. Because it must be used, it becomes an expensive device. In addition, there is a problem that the apparatus must be equipped with an extra ultraviolet light generator.
このような状況の中で、本発明者らは、上記従来技術に鑑みて、可視光に感受性を有する可視光感受性の新しい光触媒を開発することを目指して鋭意研究を積み重ねた結果、特定の酸化物と複合化した酸化ジルコニウム系複合化合物が、可視光感受性を有する新しい光機能性酸化物として使用できることを見出し、本発明を完成するに至った。 Under such circumstances, the present inventors have conducted intensive research aimed at developing a new visible light-sensitive photocatalyst having sensitivity to visible light in view of the above-described conventional technology. The present inventors have found that a zirconium oxide-based composite compound complexed with a product can be used as a new photofunctional oxide having visible light sensitivity, and completed the present invention.
本発明は、可視光感受性を有する酸化ジルコニウム含有結晶性金属化合物からなる新しい光機能性酸化物を提供することを目的とするものである。また、本発明は、太陽光エネルギーの大部分を占める可視光領域を有効に利用することができる酸化ジルコニウム系光触媒を提供することを目的とするものである。また、本発明は、紫外光を透過する材料を使用することなく、安価に光触媒装置を構築することを可能とする、可視光感受性光触媒装置を提供することを目的とするものである。また、本発明は、特殊な原料化合物を使用することなく、通常の溶液反応により簡便に可視光感受性の酸化ジルコニウム系光触媒を製造することを可能とする可視光感受性の酸化ジルコニウム系光機能性酸化物の製造方法を提供することを目的とするものである。更に、本発明は、可視光感受性の酸化ジルコニウム系光触媒製品を提供することを目的とするものである。 It is an object of the present invention to provide a new photofunctional oxide comprising a zirconium oxide-containing crystalline metal compound having visible light sensitivity. Another object of the present invention is to provide a zirconium oxide photocatalyst that can effectively use the visible light region that occupies most of the solar energy. Another object of the present invention is to provide a visible light sensitive photocatalyst device that makes it possible to construct a photocatalyst device at low cost without using a material that transmits ultraviolet light. In addition, the present invention provides a visible light sensitive zirconium oxide-based photofunctional oxidation that makes it possible to easily produce a visible light sensitive zirconium oxide-based photocatalyst by an ordinary solution reaction without using a special raw material compound. It aims at providing the manufacturing method of a thing. It is another object of the present invention to provide a visible light sensitive zirconium oxide photocatalyst product.
上記課題を解決するための本発明は、以下の技術的手段から構成される。
（１）ＺｒＯ２と、Ｍ１Ｏ５／２及びＭ２Ｏ３／２を構成成分とする光機能性酸化物であって、一般式： （ＺｒＯ２）１−ｎ［（Ｍ１Ｏ５／２）（Ｍ２Ｏ３／２）］ｎ
（式中、Ｍ１はＮｂ、Ｔａ、Ｓｂから選ばれる少なくとも一種の金属元素、Ｍ２はＣｒ、Ｆｅから選ばれる少なくとも一種の金属元素を表す。）で表される結晶性金属化合物からなることを特徴とする光機能性酸化物。
（２）結晶性金属化合物が、（ＺｒＯ２）１−ｎ（Ｍ１Ｍ２Ｏ４）ｎ（式中、ｎは０．３〜０．７である。）からなる前記（１）に記載の光機能性酸化物。
（３）結晶性金属化合物が、（ＺｒＯ２）２／３［（Ｍ１Ｏ５／２）（Ｍ２Ｏ３／２）］１／３、又は（ＺｒＯ２）１／２［（Ｍ１Ｏ５／２）（Ｍ２Ｏ３／２）］１／２である前記（１）に記載の光機能性酸化物。
（４）（Ｍ１Ｏ５／２）／（Ｍ２Ｏ３／２）＝１である前記（１）に記載の光機能性酸化物。
（５）酸化ジルコニウムの含有量が、３０〜６０モル％である前記（１）に記載の光機能性酸化物。
（６）結晶性金属化合物が、可視光感受性の光触媒作用を有する前記（１）に記載の光機能性酸化物。
（７）前記（１）から（６）のいずれかに記載の光機能性酸化物からなることを特徴とする可視光感受性を有する光触媒。
（８）前記（７）に記載の光触媒を担持させたことを特徴とする光触媒製品。
（９）ジルコニウムと、ニオブ、タンタル、アンチモンから選ばれる少なくとも一種の金属元素、及び鉄、クロムから選ばれる少なくとも一種の金属元素を所定の割合で含有する原料溶液を調製し、これにアルカリを加えて溶液のｐＨを調整することにより生成した反応生成物を仮焼することを特徴とする光機能性酸化物の製造方法。
（１０）原料溶液を加熱処理した後、アルカリを加えて溶液のｐＨを調整して沈殿物を形成させ、更に、これを加熱処理する前記（９）に記載の光機能性酸化物の製造方法。
The present invention for solving the above-described problems comprises the following technical means.
(1) A photofunctional oxide containing ZrO 2 and M 1 O 5/2 and M 2 O 3/2 as constituent components, and having a general formula: (ZrO 2 ) 1-n [(M 1 O 5 / 2 ) (M 2 O 3/2 )] n
(Wherein M 1 represents at least one metal element selected from Nb, Ta, and Sb, and M 2 represents at least one metal element selected from Cr and Fe). Photofunctional oxide characterized by
(2) The crystalline metal compound according to (1), wherein the crystalline metal compound is composed of (ZrO 2 ) 1-n (M 1 M 2 O 4 ) n (wherein n is 0.3 to 0.7). Photofunctional oxide.
(3) The crystalline metal compound is (ZrO 2 ) 2/3 [(M 1 O 5/2 ) (M 2 O 3/2 )] 1/3 or (ZrO 2 ) 1/2 [(M 1 O 5/2 ) (M 2 O 3/2 )] 1/2 The photofunctional oxide according to (1).
(4) The photofunctional oxide according to (1), wherein (M 1 O 5/2 ) / (M 2 O 3/2 ) = 1.
(5) The photofunctional oxide according to (1), wherein the content of zirconium oxide is 30 to 60 mol%.
(6) The photofunctional oxide according to (1), wherein the crystalline metal compound has a visible light sensitive photocatalytic action.
(7) A photocatalyst having visible light sensitivity, comprising the photofunctional oxide according to any one of (1) to (6).
(8) A photocatalyst product comprising the photocatalyst according to (7) supported thereon.
(9) A raw material solution containing zirconium, at least one metal element selected from niobium, tantalum, and antimony, and at least one metal element selected from iron and chromium in a predetermined ratio is prepared, and an alkali is added thereto. A method for producing a photofunctional oxide, comprising calcining a reaction product produced by adjusting the pH of the solution.
(10) The method for producing a photofunctional oxide according to (9) above, wherein the raw material solution is heat-treated, an alkali is added to adjust the pH of the solution to form a precipitate, and this is further heat-treated. .
次に、本発明について更に詳細に説明する。
本発明は、ＺｒＯ２とＭ１Ｏ５／２及びＭ２Ｏ３／２を構成成分とする光機能性酸化物であって、一般式：（ＺｒＯ２）１−ｎ［（Ｍ１Ｏ５／２）（Ｍ２Ｏ３／２）］ｎ（式中、Ｍ１はＮｂ、Ｔａ、Ｓｂから選ばれる少なくとも一種の金属元素、Ｍ２はＣｒ、Ｆｅから選ばれる少なくとも一種の金属元素を表す。）で表される結晶性金属化合物からなる紫外光及び可視光に感受性を有する光機能性酸化物、その製造方法及び光触媒製品の点、に特徴を有するものである。
Next, the present invention will be described in more detail.
The present invention is a photofunctional oxide containing ZrO 2 , M 1 O 5/2 and M 2 O 3/2 as constituent components, and has the general formula: (ZrO 2 ) 1-n [(M 1 O 5 / 2 ) (M 2 O 3/2 )] n (wherein M 1 represents at least one metal element selected from Nb, Ta, and Sb, and M 2 represents at least one metal element selected from Cr and Fe. .) Is a photofunctional oxide that is sensitive to ultraviolet light and visible light, and is characterized by its production method and photocatalytic product.
従来知られている酸化チタン光触媒の欠点は、バンドギャップが約３ｅ．Ｖと少し大きいため、４００ｎｍ以上の波長の可視光を利用できないことであり、そのために、バンドギャップを少しでも小さくすることにより、可視光域での光吸収率を高め、太陽光の利用効率を高める提案が数多くなされている。その場合、バンド構造における導電帯位置は、水素発生電位よりもある程度離れていて、例えば、ＳｒＴｉＯ３と略同じ位の位置になることが望ましい。 The disadvantage of the conventionally known titanium oxide photocatalyst is that the band gap is about 3e. Since it is a little larger than V, it is impossible to use visible light having a wavelength of 400 nm or more. Therefore, by reducing the band gap as much as possible, the light absorption rate in the visible light region is increased, and the utilization efficiency of sunlight is increased. Many proposals have been made to increase it. In that case, it is desirable that the conductive band position in the band structure is somewhat away from the hydrogen generation potential, for example, approximately the same position as SrTiO 3 .
酸化ジルコニウムは、バンドギャップが大きく、約５．０ｅ．Ｖであるが、水素還元電位は、かなり離れている。本発明者らは、バンドギャップの比較的小さい酸化物としては、Ｃｒ２Ｏ３（１．６ｅ．Ｖ）、Ｆｅ２Ｏ３酸化鉄（２．２ｅ．Ｖ）が知られていることから、これらの酸化物を組み合わせれば、３ｅ．Ｖ以下のバンドギャップで、しかも水素還元電位より−側に導電帯のある物質ができるのではないかと考えた。本発明は、こうした考えのもとに新しい光触媒材料として開発されたものであり、本発明の光機能性酸化物は、紫外光は勿論のこと可視光照射下でも光触媒作用を発揮することを実現したものである。 Zirconium oxide has a large band gap, about 5.0 e. V, but the hydrogen reduction potential is quite far away. The present inventors have known Cr 2 O 3 (1.6 eV) and Fe 2 O 3 iron oxide (2.2 eV) as oxides having a relatively small band gap. If these oxides are combined, 3e. It was thought that a substance having a band gap of V or less and having a conduction band on the negative side from the hydrogen reduction potential may be formed. The present invention was developed as a new photocatalytic material based on these ideas, and the photofunctional oxide of the present invention realizes a photocatalytic action under irradiation of visible light as well as ultraviolet light. It is a thing.
本発明は、バンドギャップの大きい酸化ジルコニウムを、Ｎｂ、Ｔａ、Ｓｂから選ばれる少なくとも一種の酸化物（Ｍ１Ｏ５／２）、及びＣｒ、Ｆｅから選ばれる少なくとも一種の酸化物（Ｍ２Ｏ３／２）とで複合化して結晶性金属化合物とすることにより、バンドギャップを小さくし、紫外光及び可視光により励起される新しい光機能性酸化物を作製することを実現するものである。本発明の光機能性酸化物は、１モルのＺｒＯ２に対して、（Ｍ１Ｏ５／２、Ｍ２Ｏ３／２）が０．４２〜２．３３モル、好適には０．５０〜１．０モルであり、Ｍ１Ｏ５／２とＭ２Ｏ３／２のモル比は１である。 In the present invention, zirconium oxide having a large band gap is obtained by using at least one oxide selected from Nb, Ta, and Sb (M 1 O 5/2 ) and at least one oxide selected from Cr and Fe (M 2 O). 3/2 ) to form a crystalline metal compound, thereby reducing the band gap and producing a new photofunctional oxide excited by ultraviolet light and visible light. The photofunctional oxide of the present invention has (M 1 O 5/2 , M 2 O 3/2 ) of 0.42 to 2.33 mol, preferably 0.50 with respect to 1 mol of ZrO 2 . The molar ratio of M 1 O 5/2 and M 2 O 3/2 is 1.
本発明の光機能性酸化物は、酸化ジルコニウムを３０〜６０モル％含み、残りがＭ１Ｏ５／２、及びＭ２Ｏ３／２からなる組成を有するものが好適である。本発明の光機能性酸化物の好適な組成物としては、例えば、（ＺｒＯ２）２／３［（Ｍ１Ｏ５／２）（Ｍ２Ｏ３／２）］１／３、又は（ＺｒＯ２）１／２［（Ｍ１Ｏ５／２）（Ｍ２Ｏ３／２）］１／２を挙げることができる。しかし、これらに制限されるものではない。本発明の光機能性酸化物は、Ｃｒ２Ｏ３及び／又はＦｅ２Ｏ３を含んでいるために、薄い褐色又は薄い青色に着色している。このため、白色の酸化チタン粉体等に比べて、可視光領域での光吸収が大きくなっている。このような可視光域での吸収が大きいことが、本発明の可視光感受性の光触媒としての効果を発現するための大きな要因である。 The photofunctional oxide of the present invention preferably contains 30 to 60 mol% of zirconium oxide, and the remainder has a composition composed of M 1 O 5/2 and M 2 O 3/2 . As a suitable composition of the photofunctional oxide of the present invention, for example, (ZrO 2 ) 2/3 [(M 1 O 5/2 ) (M 2 O 3/2 )] 1/3 , or (ZrO 2 ) 1/2 [(M 1 O 5/2 ) (M 2 O 3/2 )] 1/2 may be mentioned. However, it is not limited to these. Since the photofunctional oxide of the present invention contains Cr 2 O 3 and / or Fe 2 O 3 , it is colored light brown or light blue. For this reason, light absorption in the visible light region is larger than that of white titanium oxide powder or the like. Such a large absorption in the visible light region is a major factor for expressing the effect of the present invention as a visible light sensitive photocatalyst.
本発明の光機能性酸化物は、紫外光は勿論のこと可視光照射下でも光触媒作用を発現する。本発明の光機能性酸化物の光触媒機能を評価するために、評価テストの一つとして、青色染料のメチレンブルーを脱色させる方法により、本発明の光機能性酸化物をメチレンブルー溶液に分散して、自然光のみで青色染料を分解させたところ、これを分解脱色することが分かった。比較のために、市販の光触媒用酸化チタン粉体（Ｐ−２５）を同じ条件で試験したところ、自然光ではメチレンブルーを分解することはできなかった。 The photofunctional oxide of the present invention exhibits a photocatalytic action under irradiation of visible light as well as ultraviolet light. In order to evaluate the photocatalytic function of the photofunctional oxide of the present invention, as one of the evaluation tests, the photofunctional oxide of the present invention is dispersed in a methylene blue solution by a method of decolorizing the blue dye methylene blue, When the blue dye was decomposed only with natural light, it was found to decompose and decolor it. For comparison, when a commercially available titanium oxide powder for photocatalyst (P-25) was tested under the same conditions, methylene blue could not be decomposed by natural light.
本発明の光機能性酸化物は、ジルコニウムと、ニオブ、タンタル、アンチモンから選ばれる少なくとも一種の金属元素（Ｍ１）、及び鉄、クロムから選ばれる少なくとも一種の金属元素（Ｍ２）を所定の割合で含有する原料溶液を調製し、これにアルカリを加えて溶液のｐＨを調整することにより生成した沈殿物を仮焼することにより作製される。ジルコニウム、金属元素（Ｍ１）、及び金属元素（Ｍ２）を含む原料溶液を作製するには、所定量の金属塩、金属アルコキシド、金属等を原料として、これらを溶解して調製する。好適には、例えば、オキシ塩化ジルコニウム、オキシ硝酸ジルコニウム、硝酸ジルコニウム等の硝酸塩、塩化タンタル、五塩化アンチモン、塩化ニオビウム等の塩化物、塩化クロミウム等の水溶性クロム塩、塩化鉄等の水溶性鉄塩、金属ニオブ、金属タンタル、金属アンチモン等が使用される。 The photofunctional oxide of the present invention contains zirconium, at least one metal element (M 1 ) selected from niobium, tantalum, and antimony, and at least one metal element (M 2 ) selected from iron and chromium. It is prepared by preparing a raw material solution contained in a proportion and calcining a precipitate generated by adding alkali to the solution to adjust the pH of the solution. In order to prepare a raw material solution containing zirconium, a metal element (M 1 ), and a metal element (M 2 ), a predetermined amount of a metal salt, a metal alkoxide, a metal, or the like is used as a raw material to prepare them. Preferably, for example, nitrates such as zirconium oxychloride, zirconium oxynitrate and zirconium nitrate, chlorides such as tantalum chloride, antimony pentachloride and niobium chloride, water-soluble chromium salts such as chromium chloride, and water-soluble iron such as iron chloride Salts, metallic niobium, metallic tantalum, metallic antimony, etc. are used.
原料溶液は、水性溶媒から調製するのが好適であるが、アルコール類等の有機溶媒から調製することも適宜可能である。溶液の金属イオン濃度は、０．０１〜０．１モル％程度が好適である。こうして調製した原料溶液に、アンモニア、炭酸アンモニウム等のアルカリを添加してｐＨを調整することにより反応生成物を沈殿させるが、この場合、溶液のｐＨを９以上、好適にはｐＨを９〜１１に調整することにより、金属の水酸化物あるいは水和酸化物の沈殿を生成させることができる。 The raw material solution is preferably prepared from an aqueous solvent, but can also be appropriately prepared from an organic solvent such as alcohols. The metal ion concentration of the solution is preferably about 0.01 to 0.1 mol%. The reaction product is precipitated by adjusting the pH by adding an alkali such as ammonia or ammonium carbonate to the raw material solution thus prepared. In this case, the pH of the solution is 9 or more, preferably 9 to 11 pH. By adjusting to, a precipitate of metal hydroxide or hydrated oxide can be generated.
原料溶液は、アルカリを添加して加水分解反応を行う前に加熱処理を行うことが好適であり、例えば、８０〜１００℃で、２４〜７２時間の加熱処理、例えば、２４時間以上煮沸処理して、原料溶液を水和酸化物の懸濁状にさせることが好適である。次いで、これにアルカリを添加して加水分解物を沈殿させる。また、この場合、加水分解反応の終了後、溶液を加熱処理することが好ましく、例えば、溶液を、３０分間以上煮沸する等の加熱処理をすることが好適である。反応生成物の乾燥は、例えば、５０〜３００℃行われ、仮焼は４００〜１３００℃で２〜８時間加熱して行うことが好適である。 The raw material solution is preferably subjected to a heat treatment before adding an alkali to carry out a hydrolysis reaction. For example, the raw material solution is heated at 80 to 100 ° C. for 24 to 72 hours, for example, boiled for 24 hours or more. Thus, it is preferable to make the raw material solution into a hydrated oxide suspension. Next, an alkali is added thereto to precipitate the hydrolyzate. In this case, after completion of the hydrolysis reaction, the solution is preferably heat-treated. For example, it is preferable to heat-treat the solution such as boiling for 30 minutes or more. The reaction product is dried, for example, at 50 to 300 ° C., and the calcination is preferably performed at 400 to 1300 ° C. for 2 to 8 hours.
酸化ジルコニウムは、バンドギャップが約５．０ｅ．Ｖと大きく、また、水素還元電位が水素発生電位よりもかなりかけ離れていることから、紫外光にのみ感受性を有する光触媒特性を示す光機能性材料の一種として知られているが、光触媒としての利用はほとんど行われていなかった。これに対して、本発明は、酸化ジルコニウムと、ニオブ、タンタル、アンチモンから選ばれる少なくとも一種の金属元素、及びクロム、鉄から選ばれる少なくとも一種の金属元素を特定の割合で有することにより、酸化チタンよりもバンドギャップが大きい酸化ジルコニウムを可視光感受性の機能性酸化物とした、新規な酸化ジルコニウム系光機能性酸化物を作製し、提供することを実現するものである。 Zirconium oxide has a band gap of about 5.0 e. It is known as a kind of photofunctional material exhibiting photocatalytic properties that are sensitive only to ultraviolet light because it is large as V and the hydrogen reduction potential is far away from the hydrogen generation potential, but it is used as a photocatalyst. Was hardly done. On the other hand, the present invention includes zirconium oxide, at least one metal element selected from niobium, tantalum, and antimony, and at least one metal element selected from chromium and iron in a specific ratio. It is possible to produce and provide a novel zirconium oxide-based photofunctional oxide using zirconium oxide having a larger band gap as a visible light sensitive functional oxide.
本発明は、従来、可視光感受性の光触媒機能を付与することができなかった酸化ジルコニウムを複合化することにより、３ｅ．Ｖ以下のバンドギャップで、しかも水素還元電位より−側に導電帯を有する新規複合光機能性酸化物を作製することで、可視光領域において活性化することに成功したものであり、太陽エネルギーの有効利用を可能とし、更に、可視光感受性の光触媒作用を利用した新しい反応プロセス、装置及び光触媒製品を提供するものとして有用である。本発明は、任意の対象物の表面に上記酸化ジルコニウム系光機能性酸化物を光触媒として適宜の手段で担持させて光触媒特性を付与した光触媒製品を作製し、提供することを可能とする。 In the present invention, by combining zirconium oxide, which could not provide a visible light-sensitive photocatalytic function, 3e. By producing a novel composite photofunctional oxide having a band gap of V or less and having a conduction band on the negative side from the hydrogen reduction potential, it was successfully activated in the visible light region. It is useful for providing a new reaction process, apparatus, and photocatalyst product that enable effective use and that utilizes photocatalysis that is sensitive to visible light. The present invention makes it possible to produce and provide a photocatalyst product imparted with photocatalytic properties by supporting the above-described zirconium oxide photofunctional oxide as a photocatalyst on the surface of an arbitrary object by an appropriate means.
本発明により、（１）一般式：（ＺｒＯ２）１−ｎ［（Ｍ１Ｏ５／２）（Ｍ２Ｏ３／２）］ｎ（Ｍ１はＮｂ、Ｔａ、Ｓｂから選ばれる少なくとも一種の金属元素、Ｍ２はＣｒ、Ｆｅから選ばれる少なくとも一種の金属元素を表す。）の組成を有する結晶性金属化合物からなる新しい光機能性酸化物を提供することができる、（２）太陽光エネルギーの大部分を占める可視光領域の光により励起されて光触媒作用を発揮するジルコニウム含有結晶性金属化合物を提供することができる、（３）紫外光透過性を有する材料を使用することなく、可視光のみを透過する材料、例えば、安価な普通のガラスにより光触媒装置を構築することができる、（４）溶液沈殿反応を利用して、簡便に上記光機能性酸化物を製造することを可能とする上記光機能性酸化物の製造方法を提供することができる、（５）更に、上記酸化ジルコニウム系光機能性酸化物の光触媒作用を利用した新規な可視光感受性光触媒製品を提供することができる、という効果が奏される。 According to the present invention, (1) general formula: (ZrO 2 ) 1-n [(M 1 O 5/2 ) (M 2 O 3/2 )] n (M 1 is at least one selected from Nb, Ta, Sb) And (2) sunlight, which can provide a new photofunctional oxide comprising a crystalline metal compound having a composition of (M 2 represents at least one metal element selected from Cr and Fe). A zirconium-containing crystalline metal compound that is excited by light in the visible light region that occupies most of the energy and exhibits a photocatalytic action can be provided. (3) Visible without using a material having ultraviolet light transparency. A photocatalytic device can be constructed from a material that transmits only light, for example, inexpensive ordinary glass. (4) It is possible to easily produce the above-mentioned photofunctional oxide using a solution precipitation reaction. Do A method for producing the photofunctional oxide can be provided. (5) Furthermore, a novel visible light sensitive photocatalytic product utilizing the photocatalytic action of the zirconium oxide photofunctional oxide can be provided. The effect is played.
次に、実施例により本発明を具体的に説明するが、本発明は、これらの実施例によって何ら限定されるものではない。 EXAMPLES Next, although an Example demonstrates this invention concretely, this invention is not limited at all by these Examples.
本実施例では、（ＺｒＯ２）１−ｎ（ＣｒＮｂＯ４）ｎ、ｎ＝１／３からなる光機能性酸化物を作製した。まず、０．０２６モルのオキシ塩化ジルコニウム・８水和物、０．００６５モルの塩化ニオビウム、０．００６５モルの塩化クロミウム・６水和物の各化合物を、水２０００ｍｌに溶解して原料溶液を調製した。この水溶液を２４時間煮沸した後に、ｐＨ値が約９となるようにアンモニア水を添加して沈殿を形成させた。沈殿反応が完結した後、再度３０分間煮沸した。静置して沈殿を沈降させた後、上澄み液を除去してスプレードライ装置により乾燥して粉体を得た。この粉末を１２００℃で１時間、大気中で仮焼した後、乳鉢でほぐして平均粒径２μｍ以下の粉体とした。この粉体のＸ線回折図を図１に、反射スペクトルを図３の分光反射率曲線（Ｃｒ／Ｎｂ）に示した。これらの結果から、本発明の光機能性酸化物が、（ＺｒＯ２）２／３（ＣｒＮｂＯ４）１／３の組成を有すること、明確な結晶性を有し、可視光領域で高い光吸収を示すことが分かった。 In this example, a photofunctional oxide composed of (ZrO 2 ) 1-n (CrNbO 4 ) n and n = 1/3 was produced. First, 0.026 mol of zirconium oxychloride · 8 hydrate, 0.0065 mol of niobium chloride, 0.0065 mol of chromium chloride · hexahydrate were dissolved in 2000 ml of water to prepare a raw material solution. Prepared. After boiling this aqueous solution for 24 hours, aqueous ammonia was added to form a precipitate so that the pH value was about 9. After the precipitation reaction was completed, it was boiled again for 30 minutes. After allowing to stand to settle the precipitate, the supernatant was removed and dried with a spray dryer to obtain a powder. This powder was calcined in the atmosphere at 1200 ° C. for 1 hour and then loosened in a mortar to obtain a powder having an average particle size of 2 μm or less. The X-ray diffraction pattern of this powder is shown in FIG. 1, and the reflection spectrum is shown in the spectral reflectance curve (Cr / Nb) of FIG. From these results, the photofunctional oxide of the present invention has a composition of (ZrO 2 ) 2/3 (CrNbO 4 ) 1/3 , clear crystallinity, and high light absorption in the visible light region. It was found that
本実施例では、（ＺｒＯ２）１−ｎ（ＦｅＮｂＯ４）ｎ、ｎ＝１／３からなる光機能性酸化物を作製した。０．０２６モルのオキシ塩化ジルコニウム・８水和物、０．００６５モルの塩化ニオビウム、０．００６５ルの塩化鉄・６水和物の各化合物を、水２０００ｍｌに溶解して原料溶液を調製した。この水溶液を４８時間煮沸した後に、ｐＨ値が約９となるように、アンモニア水を添加して沈殿を形成させた。沈殿反応が完結した後、再度６０分間煮沸した。静置して沈殿を沈降させた後、上澄み液を除去してスプレードライ装置により乾燥して粉体を得た。この粉末を１２００℃で１時間、大気中で仮焼した後、乳鉢でほぐして平均粒径２μｍ以下の粉体とした。図２に、この粉体のＸ線回折図を示した。また、図３に、この粉体の分光反射率曲線（Ｆｅ／Ｎｂ）を示した。これらの結果から、得られた生成物が（ＺｒＯ２）２／３（ＦｅＮｂＯ４）１／３の組成を有すること、明確な結晶性を有し、可視光領域で高い光吸収性を示すこと、が分かった。 In this example, a photofunctional oxide composed of (ZrO 2 ) 1-n (FeNbO 4 ) n and n = 1/3 was produced. 0.026 mol of zirconium oxychloride / octahydrate, 0.0065 mol of niobium chloride and 0.0065 mol of iron chloride / hexahydrate were dissolved in 2000 ml of water to prepare a raw material solution. . After boiling this aqueous solution for 48 hours, ammonia water was added to form a precipitate so that the pH value was about 9. After the precipitation reaction was completed, it was boiled again for 60 minutes. After allowing to stand to settle the precipitate, the supernatant was removed and dried with a spray dryer to obtain a powder. This powder was calcined in the atmosphere at 1200 ° C. for 1 hour and then loosened in a mortar to obtain a powder having an average particle size of 2 μm or less. FIG. 2 shows an X-ray diffraction pattern of this powder. FIG. 3 shows the spectral reflectance curve (Fe / Nb) of this powder. From these results, the obtained product has a composition of (ZrO 2 ) 2/3 (FeNbO 4 ) 1/3 , clear crystallinity, and high light absorption in the visible light region. I understand.
本実施例では、（ＺｒＯ２）１−ｎ（ＦｅＴａＯ４）ｎ、ｎ＝１／３からなる光機能性酸化物を作製した。０．０２６モルのオキシ塩化ジルコニウム・８水和物、０．００６５モルの塩化タンタル、０．００６５モルの塩化鉄・６水和物の各化合物を、水２０００ｍｌに溶解して原料溶液を調製した以外は、実施例１と同様にして、光機能性酸化物を作製した。 In this example, a photofunctional oxide composed of (ZrO 2 ) 1-n (FeTaO 4 ) n , n = 1/3 was produced. 0.026 mol of zirconium oxychloride octahydrate, 0.0065 mol of tantalum chloride and 0.0065 mol of iron chloride hexahydrate were dissolved in 2000 ml of water to prepare a raw material solution. Except for the above, a photofunctional oxide was produced in the same manner as in Example 1.
本実施例では、（ＺｒＯ２）１−ｎ（ＣｒＴａＯ４）ｎ、ｎ＝１／３からなる光機能性酸化物を作製した。０．０２６モルのオキシ塩化ジルコニウム・８水和物、０．００６５モルの塩化タンタル、０．００６５モルの塩化クロミウム・６水和物の各化合物を、水２０００ｍｌに溶解して原料溶液を調製した以外は、実施例１と同様にして、光機能性酸化物を作製した。 In this example, a photofunctional oxide composed of (ZrO 2 ) 1-n (CrTaO 4 ) n and n = 1/3 was produced. 0.026 mol of zirconium oxychloride octahydrate, 0.0065 mol of tantalum chloride and 0.0065 mol of chromium chloride hexahydrate were dissolved in 2000 ml of water to prepare a raw material solution. Except for the above, a photofunctional oxide was produced in the same manner as in Example 1.
本実施例では、（ＺｒＯ２）１−ｎ（Ｃｒ０．５Ｆｅ０．５ＴａＯ４）ｎ、ｎ＝１／３からなる光機能性酸化物を作製した。０．０２６モルのオキシ塩化ジルコニウム・８水和物、０．００６５モルの塩化タンタル、０．００３３モルの塩化クロミウム・６水和物、０．００３３モルの塩化鉄・６水和物の各化合物を、水２０００ｍｌに溶解して原料溶液を調製した以外は、実施例１と同様にして、光機能性酸化物を作製した。 In this example, a photofunctional oxide composed of (ZrO 2 ) 1-n (Cr 0.5 Fe 0.5 TaO 4 ) n and n = 1/3 was produced. 0.026 mol zirconium oxychloride octahydrate, 0.0065 mol tantalum chloride, 0.0033 mol chromium chloride hexahydrate, 0.0033 mol iron chloride hexahydrate Was dissolved in 2000 ml of water to prepare a raw material solution, and a photofunctional oxide was produced in the same manner as in Example 1.
本実施例では、（ＺｒＯ２）１−ｎ（ＣｒＮｂＯ４）ｎ、ｎ＝１／２からなる光機能性酸化物を作製した。０．０２モルのオキシ塩化ジルコニウム・８水和物、０．０１モルの塩化ニオビウム、０．０１モルの塩化クロミウム・６水和物の各化合物を、水２０００ｍｌに溶解して原料溶液を調製した。乾燥した粉体を８００℃、２時間、大気中で仮焼した以外は、実施例１と同様にして、光機能性酸化物を作製した。 In this example, an optical functional oxide composed of (ZrO 2 ) 1-n (CrNbO 4 ) n and n = 1/2 was produced. 0.02 mol of zirconium oxychloride / octahydrate, 0.01 mol of niobium chloride, 0.01 mol of chromium chloride / hexahydrate were dissolved in 2000 ml of water to prepare a raw material solution. . A photofunctional oxide was produced in the same manner as in Example 1 except that the dried powder was calcined in the air at 800 ° C. for 2 hours.
本実施例では、（ＺｒＯ２）１−ｎ（ＣｒＴａＯ４）ｎ、ｎ＝１／２からなる光機能性酸化物を作製した。０．０２モルのオキシ塩化ジルコニウム・８水和物、０．０１モルの塩化タンタル、０．０１モルの塩化クロミウム・６水和物の各化合物を、水２０００ｍｌに溶解して原料溶液を調製した。乾燥した粉体を８００℃、２時間、大気中で仮焼した以外は、実施例１と同様にして、光機能性酸化物を作製した。 In this example, a photofunctional oxide composed of (ZrO 2 ) 1-n (CrTaO 4 ) n and n = 1/2 was produced. 0.02 mol zirconium oxychloride octahydrate, 0.01 mol tantalum chloride, 0.01 mol chromium chloride hexahydrate were dissolved in 2000 ml of water to prepare a raw material solution. . A photofunctional oxide was produced in the same manner as in Example 1 except that the dried powder was calcined in the air at 800 ° C. for 2 hours.
本実施例では、（ＺｒＯ２）１−ｎ（ＣｒＳｂＯ４）ｎ、ｎ＝１／２からなる光機能性酸化物を作製した。０．０２モルのオキシ塩化ジルコニウム・８水和物、０．０１モルの塩化アンチモン、０．０１モルの塩化クロミウム・６水和物の各化合物を、水２０００ｍｌに溶解して原料溶液を調製した。乾燥した粉体を８００℃、２時間、大気中で仮焼した以外は、実施例１と同様にして、光機能性酸化物を作製した。 In this example, an optical functional oxide composed of (ZrO 2 ) 1-n (CrSbO 4 ) n and n = 1/2 was produced. 0.02 mol of zirconium oxychloride / octahydrate, 0.01 mol of antimony chloride, 0.01 mol of chromium chloride / hexahydrate were dissolved in 2000 ml of water to prepare a raw material solution. . A photofunctional oxide was produced in the same manner as in Example 1 except that the dried powder was calcined in the air at 800 ° C. for 2 hours.
本実施例では、（ＺｒＯ２）１−ｎ（ＦｅＳｂＯ４）ｎ、ｎ＝１／２からなる光機能性酸化物を作製した。０．０２モルのオキシ塩化ジルコニウム・８水和物、０．０１モルの塩化アンチモン、０．０１モルの塩化鉄・６水和物の各化合物を、水２０００ｍｌに溶解して原料溶液を調製した。乾燥した粉体を８００℃、４時間、大気中で仮焼した以外は、実施例１と同様にして、光機能性酸化物を作製した。 In this example, an optical functional oxide composed of (ZrO 2 ) 1-n (FeSbO 4 ) n and n = 1/2 was produced. 0.02 mol of zirconium oxychloride / octahydrate, 0.01 mol of antimony chloride, 0.01 mol of iron chloride / hexahydrate were dissolved in 2000 ml of water to prepare a raw material solution. . A photofunctional oxide was produced in the same manner as in Example 1 except that the dried powder was calcined in the air at 800 ° C. for 4 hours.
実施例１及び２で作製した光機能性酸化物粉体（実施例１：Ｚｒ−Ｃｒ−Ｎｂ、実施例２：Ｚｒ−Ｆｅ−Ｎｂ）の夫々０．３ｇを、１０ｐｐｍのメチレンブルー水溶液３０ｍｌ中に攪拌、分散させて、室内に放置して、その脱色を観察した。比較のために、Ｐ−２５（デグッサ社製ＴｉＯ２）と、ＴＺ８ＹＳ（東ソー社製ＺｒＯ２）を、メチレンブルー水溶液中に分散させて、同様にして、脱色を観察した。１日放置後の脱色状態を図４に示した。実施例１及び２で作製した本発明の光機能性酸化物は、ほぼ完全にメチレンブルーを脱色したが、比較例では脱色しなかった。なお、この試験では、紫外光を透過し難い普通のガラス瓶を用いた。 0.3 g of each of the photofunctional oxide powders prepared in Examples 1 and 2 (Example 1: Zr—Cr—Nb, Example 2: Zr—Fe—Nb) was added to 30 ml of 10 ppm methylene blue aqueous solution. The mixture was stirred and dispersed and left in the room to observe decolorization. For comparison, P-25 (TiO 2 manufactured by Degussa) and TZ8YS (ZrO 2 manufactured by Tosoh Corporation) were dispersed in an aqueous methylene blue solution, and decolorization was observed in the same manner. The decolored state after standing for 1 day is shown in FIG. The photofunctional oxide of the present invention produced in Examples 1 and 2 decolorized methylene blue almost completely, but did not decolor in the comparative example. In this test, an ordinary glass bottle that hardly transmits ultraviolet light was used.
実施例１で作製した光機能性酸化物粉体０．５ｇを普通のガラス瓶に入れ、０．１ｎのヨウ化カリ（ＫＩ）溶液５０ｍｌを加えて分散させ、約２時間、窓際において自然光に当てた後、光触媒機能によるヨー素の析出状態を溶液中にデンプン溶液を滴下して観察した。その結果、本発明の光機能性酸化物の試料では、ヨウ素析出により紫色に着色し、本発明の酸化物粉体がヨウ素イオンを酸化したことが証明された。 Place 0.5 g of the photofunctional oxide powder prepared in Example 1 in an ordinary glass bottle, add 50 ml of 0.1 n potassium iodide (KI) solution and disperse it, and expose it to natural light at the window for about 2 hours. Thereafter, the precipitation state of iodine due to the photocatalytic function was observed by dropping the starch solution into the solution. As a result, the sample of the photofunctional oxide of the present invention was colored purple by iodine precipitation, and it was proved that the oxide powder of the present invention oxidized iodine ions.
以上詳述したように、本発明は、一般式：（ＺｒＯ２）１−ｎ［（Ｍ１Ｏ５／２）（Ｍ２Ｏ３／２）］ｎ（式中、Ｍ１はＮｂ、Ｔａ、Ｓｂから選ばれる少なくとも一種の金属元素、Ｍ２はＣｒ、Ｆｅから選ばれる少なくとも一種の金属元素を表す。）で表される結晶性金属化合物からなる新しい光機能性酸化物、その製造方法及びその光触媒製品に係るものであり、本発明により、可視光による光触媒作用を有するジルコニウム含有結晶性金属化合物を製造し、提供することができる。また、本発明により、太陽エネルギーの９５％を占める可視光領域を有効利用し、太陽光の利用効率を高めることが可能な新しい光機能性酸化物を提供することができる。更に、本発明は、可視光の照射を受けて発現される光触媒作用を利用した光触媒装置、その製品及び反応プロセス等を提供することができる。本発明は、可視光感受性の新規酸化ジルコニウム系光機能性酸化物及び光触媒に関する新技術・新製品を提供するものとして有用である。 As described in detail above, the present invention provides a general formula: (ZrO 2 ) 1-n [(M 1 O 5/2 ) (M 2 O 3/2 )] n (wherein M 1 is Nb, Ta , At least one metal element selected from Sb, M 2 represents at least one metal element selected from Cr and Fe.), A new photofunctional oxide comprising a crystalline metal compound represented by According to the present invention, a zirconium-containing crystalline metal compound having a photocatalytic action by visible light can be produced and provided. In addition, according to the present invention, it is possible to provide a new optical functional oxide capable of effectively using the visible light region occupying 95% of the solar energy and improving the utilization efficiency of sunlight. Furthermore, the present invention can provide a photocatalytic device utilizing a photocatalytic action that is expressed by irradiation with visible light, a product thereof, a reaction process, and the like. INDUSTRIAL APPLICATION This invention is useful as what provides the new technique and new product regarding the novel zirconium oxide type photofunctional oxide and photocatalyst which are sensitive to visible light.
Claims (10)
（式中、Ｍ１はＮｂ、Ｔａ、Ｓｂから選ばれる少なくとも一種の金属元素、Ｍ２はＣｒ、Ｆｅから選ばれる少なくとも一種の金属元素を表す。）で表される結晶性金属化合物からなることを特徴とする光機能性酸化物。 ZrO 2 , a photofunctional oxide containing M 1 O 5/2 and M 2 O 3/2 as constituents, having the general formula: (ZrO 2 ) 1-n [(M 1 O 5/2 ) (M 2 O 3/2 )] n
(Wherein M 1 represents at least one metal element selected from Nb, Ta, and Sb, and M 2 represents at least one metal element selected from Cr and Fe). Photofunctional oxide characterized by
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| WO2011111800A1 (en) | 2010-03-12 | 2011-09-15 | 株式会社オハラ | Photocatalyst, slurry mixture, forming member and coating, coating film forming member, sintered body, glass-ceramic composite, glass, building material and clarification material |
| JP2012176332A (en) * | 2011-02-25 | 2012-09-13 | Green Chemy:Kk | Visible light response photocatalyst, method for manufacturing the same and method for using the same |
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