JP2909403B2 - Titanium oxide for photocatalyst and method for producing the same - Google Patents
Titanium oxide for photocatalyst and method for producing the sameInfo
- Publication number
- JP2909403B2 JP2909403B2 JP7043582A JP4358295A JP2909403B2 JP 2909403 B2 JP2909403 B2 JP 2909403B2 JP 7043582 A JP7043582 A JP 7043582A JP 4358295 A JP4358295 A JP 4358295A JP 2909403 B2 JP2909403 B2 JP 2909403B2
- Authority
- JP
- Japan
- Prior art keywords
- titanium oxide
- titanium
- iron
- compound
- iron compound
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims description 242
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 title claims description 234
- 239000011941 photocatalyst Substances 0.000 title claims description 70
- 238000004519 manufacturing process Methods 0.000 title claims description 11
- 150000002506 iron compounds Chemical class 0.000 claims description 93
- 239000002245 particle Substances 0.000 claims description 59
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 45
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 37
- 239000011707 mineral Substances 0.000 claims description 37
- 238000000034 method Methods 0.000 claims description 34
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 32
- 239000002253 acid Substances 0.000 claims description 31
- 239000007864 aqueous solution Substances 0.000 claims description 28
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 20
- 150000003609 titanium compounds Chemical class 0.000 claims description 20
- 239000000243 solution Substances 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- 238000006460 hydrolysis reaction Methods 0.000 claims description 11
- 230000007062 hydrolysis Effects 0.000 claims description 10
- 238000006386 neutralization reaction Methods 0.000 claims description 6
- 230000003301 hydrolyzing effect Effects 0.000 claims description 5
- 238000009835 boiling Methods 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 3
- 230000003647 oxidation Effects 0.000 claims description 3
- 238000007254 oxidation reaction Methods 0.000 claims description 3
- 229910052719 titanium Inorganic materials 0.000 claims description 3
- 239000010936 titanium Substances 0.000 claims description 3
- 230000001699 photocatalysis Effects 0.000 description 36
- 239000000725 suspension Substances 0.000 description 30
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 27
- 235000014413 iron hydroxide Nutrition 0.000 description 27
- NCNCGGDMXMBVIA-UHFFFAOYSA-L iron(ii) hydroxide Chemical compound [OH-].[OH-].[Fe+2] NCNCGGDMXMBVIA-UHFFFAOYSA-L 0.000 description 27
- 239000000126 substance Substances 0.000 description 16
- 229910000349 titanium oxysulfate Inorganic materials 0.000 description 16
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 15
- 230000000052 comparative effect Effects 0.000 description 13
- 239000013078 crystal Substances 0.000 description 13
- 238000013032 photocatalytic reaction Methods 0.000 description 13
- 239000000047 product Substances 0.000 description 13
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 12
- 230000002378 acidificating effect Effects 0.000 description 12
- 238000010306 acid treatment Methods 0.000 description 11
- 239000000203 mixture Substances 0.000 description 10
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 9
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 description 8
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 8
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 7
- 238000000354 decomposition reaction Methods 0.000 description 7
- 229910017604 nitric acid Inorganic materials 0.000 description 7
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- 229910000358 iron sulfate Inorganic materials 0.000 description 6
- NQXWGWZJXJUMQB-UHFFFAOYSA-K iron trichloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].Cl[Fe+]Cl NQXWGWZJXJUMQB-UHFFFAOYSA-K 0.000 description 6
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 6
- -1 platinum and rhodium Chemical class 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 239000003513 alkali Substances 0.000 description 5
- 238000010304 firing Methods 0.000 description 5
- 238000010335 hydrothermal treatment Methods 0.000 description 5
- 235000013980 iron oxide Nutrition 0.000 description 5
- DCKVFVYPWDKYDN-UHFFFAOYSA-L oxygen(2-);titanium(4+);sulfate Chemical compound [O-2].[Ti+4].[O-]S([O-])(=O)=O DCKVFVYPWDKYDN-UHFFFAOYSA-L 0.000 description 5
- 230000001443 photoexcitation Effects 0.000 description 5
- 229910000348 titanium sulfate Inorganic materials 0.000 description 5
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- CUPCBVUMRUSXIU-UHFFFAOYSA-N [Fe].OOO Chemical compound [Fe].OOO CUPCBVUMRUSXIU-UHFFFAOYSA-N 0.000 description 4
- 150000001412 amines Chemical class 0.000 description 4
- 229910021529 ammonia Inorganic materials 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 description 4
- 229910021519 iron(III) oxide-hydroxide Inorganic materials 0.000 description 4
- 230000003472 neutralizing effect Effects 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- LLZRNZOLAXHGLL-UHFFFAOYSA-J titanic acid Chemical compound O[Ti](O)(O)O LLZRNZOLAXHGLL-UHFFFAOYSA-J 0.000 description 4
- 238000007796 conventional method Methods 0.000 description 3
- PVFSDGKDKFSOTB-UHFFFAOYSA-K iron(3+);triacetate Chemical compound [Fe+3].CC([O-])=O.CC([O-])=O.CC([O-])=O PVFSDGKDKFSOTB-UHFFFAOYSA-K 0.000 description 3
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 3
- 150000002896 organic halogen compounds Chemical class 0.000 description 3
- 230000001590 oxidative effect Effects 0.000 description 3
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical class [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- 241000186361 Actinobacteria <class> Species 0.000 description 2
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 2
- 241000894006 Bacteria Species 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- 241000195493 Cryptophyta Species 0.000 description 2
- 241000233866 Fungi Species 0.000 description 2
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 2
- 229910002651 NO3 Inorganic materials 0.000 description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 230000002411 adverse Effects 0.000 description 2
- 150000001299 aldehydes Chemical class 0.000 description 2
- 239000001099 ammonium carbonate Substances 0.000 description 2
- 235000012501 ammonium carbonate Nutrition 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 239000002270 dispersing agent Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- RAQDACVRFCEPDA-UHFFFAOYSA-L ferrous carbonate Chemical compound [Fe+2].[O-]C([O-])=O RAQDACVRFCEPDA-UHFFFAOYSA-L 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 2
- MVFCKEFYUDZOCX-UHFFFAOYSA-N iron(2+);dinitrate Chemical compound [Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MVFCKEFYUDZOCX-UHFFFAOYSA-N 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 229910017464 nitrogen compound Inorganic materials 0.000 description 2
- 150000002830 nitrogen compounds Chemical class 0.000 description 2
- 150000002903 organophosphorus compounds Chemical class 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 229910052703 rhodium Inorganic materials 0.000 description 2
- 239000010948 rhodium Substances 0.000 description 2
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 2
- 229910001925 ruthenium oxide Inorganic materials 0.000 description 2
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(iv) oxide Chemical compound O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 description 2
- 239000013076 target substance Substances 0.000 description 2
- YPFNIPKMNMDDDB-UHFFFAOYSA-K 2-[2-[bis(carboxylatomethyl)amino]ethyl-(2-hydroxyethyl)amino]acetate;iron(3+) Chemical compound [Fe+3].OCCN(CC([O-])=O)CCN(CC([O-])=O)CC([O-])=O YPFNIPKMNMDDDB-UHFFFAOYSA-K 0.000 description 1
- AWFYPPSBLUWMFQ-UHFFFAOYSA-N 2-[5-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]-1,3,4-oxadiazol-2-yl]-1-(1,4,6,7-tetrahydropyrazolo[4,3-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C1=NN=C(O1)CC(=O)N1CC2=C(CC1)NN=C2 AWFYPPSBLUWMFQ-UHFFFAOYSA-N 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- 208000035985 Body Odor Diseases 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical class S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- 241000208125 Nicotiana Species 0.000 description 1
- 235000002637 Nicotiana tabacum Nutrition 0.000 description 1
- CYTYCFOTNPOANT-UHFFFAOYSA-N Perchloroethylene Chemical group ClC(Cl)=C(Cl)Cl CYTYCFOTNPOANT-UHFFFAOYSA-N 0.000 description 1
- 206010040904 Skin odour abnormal Diseases 0.000 description 1
- 239000004115 Sodium Silicate Substances 0.000 description 1
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical group ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000004520 agglutination Effects 0.000 description 1
- 238000003915 air pollution Methods 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001447 alkali salts Chemical class 0.000 description 1
- 150000001413 amino acids Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- 150000001845 chromium compounds Chemical class 0.000 description 1
- 238000010411 cooking Methods 0.000 description 1
- 239000002781 deodorant agent Substances 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- XPPKVPWEQAFLFU-UHFFFAOYSA-N diphosphoric acid Chemical compound OP(O)(=O)OP(O)(O)=O XPPKVPWEQAFLFU-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000000417 fungicide Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 239000000383 hazardous chemical Substances 0.000 description 1
- 239000004009 herbicide Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000002917 insecticide Substances 0.000 description 1
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 description 1
- 159000000014 iron salts Chemical class 0.000 description 1
- VBMVTYDPPZVILR-UHFFFAOYSA-N iron(2+);oxygen(2-) Chemical class [O-2].[Fe+2] VBMVTYDPPZVILR-UHFFFAOYSA-N 0.000 description 1
- JCDAAXRCMMPNBO-UHFFFAOYSA-N iron(3+);oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[Ti+4].[Ti+4].[Fe+3].[Fe+3] JCDAAXRCMMPNBO-UHFFFAOYSA-N 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 239000005645 nematicide Substances 0.000 description 1
- 229910000480 nickel oxide Inorganic materials 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 235000011007 phosphoric acid Nutrition 0.000 description 1
- 150000003071 polychlorinated biphenyls Chemical group 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 229940005657 pyrophosphoric acid Drugs 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 235000019795 sodium metasilicate Nutrition 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 230000001954 sterilising effect Effects 0.000 description 1
- 238000004659 sterilization and disinfection Methods 0.000 description 1
- 150000003464 sulfur compounds Chemical class 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229950011008 tetrachloroethylene Drugs 0.000 description 1
- POWFTOSLLWLEBN-UHFFFAOYSA-N tetrasodium;silicate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-][Si]([O-])([O-])[O-] POWFTOSLLWLEBN-UHFFFAOYSA-N 0.000 description 1
- YONPGGFAJWQGJC-UHFFFAOYSA-K titanium(iii) chloride Chemical compound Cl[Ti](Cl)Cl YONPGGFAJWQGJC-UHFFFAOYSA-K 0.000 description 1
- UBOXGVDOUJQMTN-UHFFFAOYSA-N trichloroethylene Natural products ClCC(Cl)Cl UBOXGVDOUJQMTN-UHFFFAOYSA-N 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- 239000012808 vapor phase Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Exhaust Gas Treatment By Means Of Catalyst (AREA)
- Catalysts (AREA)
Description
【０００１】[0001]
【産業上の利用分野】本発明は優れた光触媒機能を有す
る酸化チタンおよびその製造方法に関する。The present invention relates to a titanium oxide having an excellent photocatalytic function and a method for producing the same.
【０００２】[0002]
【従来の技術】酸化チタンにそのバンドギャップ以上の
エネルギーを持つ波長の光を照射すると光励起により伝
導帯に電子を、価電子帯に正孔を生じる。この光励起に
より生じた電子の持つ強い還元力や正孔の持つ強い酸化
力は、有害物質の分解・浄化、アンモニア、アルデヒド
類、アミン類などの悪臭ガスの脱臭のほか、水の分解、
細菌、放線菌、菌類、藻類などの殺菌・殺藻などの光触
媒反応に利用されている。たとえば、特公平２−９８５
０号公報には、酸化チタンなどの光触媒を用いて廃棄物
中の有害物質を分解し、浄化することが記載されてい
る。また、特公平４−７８３２６号公報には、酸化チタ
ンなどの光触媒を用いてトイレのし尿臭、ペットの臭
い、たばこの臭い、調理臭、体臭などを脱臭することが
記載されている。さらに、特公平４−２９３９３号公報
には、光照射により酸化チタンなどの光触媒に生起した
所定電圧を細胞に接触印可して細胞を殺すことが記載さ
れている。2. Description of the Related Art When titanium oxide is irradiated with light having a wavelength having an energy greater than the band gap, electrons are generated in a conduction band and holes are generated in a valence band by photoexcitation. The strong reducing power of electrons generated by this photoexcitation and the strong oxidizing power of holes are used to decompose and purify harmful substances, deodorize odorous gases such as ammonia, aldehydes and amines, as well as decompose water,
It is used for photocatalytic reactions such as sterilization and algicidation of bacteria, actinomycetes, fungi and algae. For example, Japanese Patent Publication 2-985
No. 0 describes decomposing and purifying harmful substances in waste using a photocatalyst such as titanium oxide. Further, Japanese Patent Publication No. 4-78326 discloses that a photocatalyst such as titanium oxide is used to deodorize toilet odor, pet odor, tobacco odor, cooking odor, body odor, and the like. Furthermore, Japanese Patent Publication No. 4-29393 describes that a predetermined voltage generated in a photocatalyst such as titanium oxide by light irradiation is applied to cells to kill the cells.
【０００３】[0003]
【発明が解決しようとする課題】前記の光触媒反応に用
いる酸化チタンは、光触媒反応の処理時間を短縮した
り、光触媒反応に用いる装置を小型化したりするため、
一層優れた光触媒機能を有する酸化チタンが嘱望されて
いる。このような酸化チタンとしては、前記の特公平２
−９８５０号公報には、白金、ロジウムなどの金属や酸
化ニッケル、酸化ルテニウムの金属酸化物を担持した酸
化チタンが開示されている。しかしながら、酸化チタン
の表面に担持した白金、ロジウム、酸化ルテニウムなど
は高価であるため製造コストが甚大となること、担持し
た金属が光触媒反応中に溶出することなどの問題があ
る。特公平４−７８３２６号公報には、酸化チタンとチ
タン酸鉄、酸化鉄などとの混合酸化物が提案されている
が、その光触媒機能は充分満足できるものではない。The titanium oxide used in the photocatalytic reaction is used to shorten the processing time of the photocatalytic reaction or to reduce the size of the apparatus used for the photocatalytic reaction.
There is a demand for titanium oxide having a more excellent photocatalytic function. As such titanium oxide, the above-mentioned Tokuhei 2
Japanese Patent No. 9850 discloses a titanium oxide supporting a metal oxide such as platinum and rhodium, and a metal oxide such as nickel oxide and ruthenium oxide. However, platinum, rhodium, ruthenium oxide, and the like carried on the surface of titanium oxide are expensive, so that the production cost becomes enormous, and the carried metal elutes during the photocatalytic reaction. Japanese Patent Publication No. 4-78326 proposes a mixed oxide of titanium oxide and iron titanate, iron oxide or the like, but its photocatalytic function is not sufficiently satisfactory.
【０００４】[0004]
【課題を解決するための手段】本発明者らは、優れた光
触媒機能を有し、かつ、廉価な酸化チタン光触媒を得る
べく研究した結果、（１）酸化チタン粒子の内部および
／またはその表面に鉄化合物を含有させると、酸化チタ
ン単一のものや酸化チタンと鉄化合物との混合物に比
べ、光触媒機能が向上すること、しかも、このものを廉
価に製造できること、（２）酸化チタンを鉱酸処理する
と光触媒機能が向上すること、（３）鉱酸処理を施した
酸化チタン粒子の内部および／またはその表面に鉄化合
物を含有させると、さらに光触媒機能が向上することな
どを見出し、本発明を完成した。すなわち、本発明は優
れた光触媒機能を有する酸化チタン光触媒およびその製
造方法を提供することにある。The present inventors have studied to obtain an inexpensive titanium oxide photocatalyst having an excellent photocatalytic function, and as a result, (1) the inside of titanium oxide particles and / or the surface thereof. Incorporation of an iron compound in the titanium oxide improves the photocatalytic function as compared with a single titanium oxide or a mixture of titanium oxide and an iron compound, and can be manufactured at a low cost. It has been found that the photocatalytic function is improved by the acid treatment, and (3) the photocatalytic function is further improved by adding an iron compound to the inside and / or the surface of the titanium oxide particles subjected to the mineral acid treatment. Was completed. That is, an object of the present invention is to provide a titanium oxide photocatalyst having an excellent photocatalytic function and a method for producing the same.
【０００５】本発明は、鉄化合物を含有してなる酸化チ
タン光触媒に関する。本発明の酸化チタン光触媒は、酸
化チタンと鉄化合物との単なる混合物とは異なり、酸化
チタン粒子の内部に鉄化合物が取り込まれている状態お
よび／または酸化チタン粒子の表面に鉄化合物が担持さ
れている状態を保持した粒子である。本発明において、
酸化チタンとはアナタース型酸化チタン、ルチル型酸化
チタン、無定形酸化チタン、メタチタン酸、オルソチタ
ン酸などの各種の酸化チタンあるいは水酸化チタン、含
水酸化チタン、水和酸化チタンを意味する。本発明にお
いては、アナタース型酸化チタンが優れた光触媒機能を
有するため好ましい。酸化チタンの平均粒子径は、Ｓｃ
ｈｅｒｒｅｒの式より算出したり、電子顕微鏡で観察し
たりして求めることができる。本発明においては、好ま
しくは１〜５００ｎｍ、より好ましくは５〜２５０ｎ
ｍ、もっとも好ましくは５〜５０ｎｍである。また、鉄
化合物とは、酸化鉄、水酸化鉄、オキシ水酸化鉄のほ
か、硫酸鉄、塩化鉄、硝酸鉄、炭酸鉄、酢酸鉄などの鉄
塩や鉄イオンを含む。本発明においては、三価および／
または二価の鉄の化合物が一般的であり、酸化チタンの
光触媒機能を向上させるうえから好ましく、たとえば、
酸化鉄（Ｆｅ2 Ｏ3 、Ｆｅ3 Ｏ4 ）、水酸化鉄（Ｆｅ
（ＯＨ）2 、Ｆｅ（ＯＨ）3 ）、オキシ水酸化鉄（Ｆｅ
ＯＯＨ）が好ましいものである。鉄化合物の量は、対象
とする光触媒反応により任意に変えられるが、酸化チタ
ン粒子のＴｉＯ2 重量基準に対して、鉄化合物をＦｅ基
準に換算して０．０００５〜１０重量％、好ましくは
０．００１〜５重量％、より好ましくは０．００１〜３
重量％、もっとも好ましくは０．００１〜１重量％であ
る。鉄化合物が前記範囲より少なかったり、また逆に多
かったりすると光触媒機能が低下する傾向にある。The present invention relates to a titanium oxide photocatalyst containing an iron compound. The titanium oxide photocatalyst of the present invention is different from a mere mixture of titanium oxide and an iron compound in a state where the iron compound is incorporated into the titanium oxide particles and / or the iron compound is supported on the surface of the titanium oxide particles. Particles that keep their state. In the present invention,
Titanium oxide means various titanium oxides such as anatase-type titanium oxide, rutile-type titanium oxide, amorphous titanium oxide, metatitanic acid and orthotitanic acid, or titanium hydroxide, hydrous titanium oxide and hydrated titanium oxide. In the present invention, anatase-type titanium oxide is preferable because it has an excellent photocatalytic function. The average particle diameter of titanium oxide is Sc
It can be calculated by the Herrer's formula or by observation with an electron microscope. In the present invention, preferably 1 to 500 nm, more preferably 5 to 250 n
m, most preferably from 5 to 50 nm. The iron compound includes iron salts such as iron sulfate, iron chloride, iron nitrate, iron carbonate, iron acetate, and iron ions, in addition to iron oxide, iron hydroxide, and iron oxyhydroxide. In the present invention, trivalent and / or trivalent
Or a divalent iron compound is generally preferred from the viewpoint of improving the photocatalytic function of titanium oxide, for example,
Iron oxide (Fe 2 O 3 , Fe 3 O 4 ), iron hydroxide (Fe
(OH) 2 , Fe (OH) 3 ), iron oxyhydroxide (Fe
OOH) is preferred. The amount of iron compound is changed arbitrarily by the photocatalytic reaction of interest, relative to TiO 2 by weight of titanium oxide particles, the iron compound in terms of Fe based 0.0005 wt%, preferably 0 0.001 to 5% by weight, more preferably 0.001 to 3
% By weight, most preferably 0.001 to 1% by weight. If the amount of the iron compound is less than the above range or, conversely, the amount thereof is more, the photocatalytic function tends to decrease.
【０００６】本発明においては、酸化チタン光触媒に含
まれる鉄化合物は、酸化チタン粒子の表面に担持されて
いる状態が好ましく、この場合の鉄化合物の担持量は酸
化チタン粒子の表面積１ｍ2 当たり、鉄化合物をＦｅ基
準に換算して０．０５〜５０００μｇ、好ましくは０．
１〜３０００μｇ、より好ましくは０．１〜２０００μ
ｇ、もっとも好ましくは０．３〜１０００μｇである。
鉄化合物が前記範囲より少なかったり、また逆に多かっ
たりすると光触媒機能が低下する傾向にある。In the present invention, the iron compound contained in the titanium oxide photocatalyst is preferably supported on the surface of the titanium oxide particles. In this case, the amount of the iron compound supported is per 1 m 2 of the surface area of the titanium oxide particles. The iron compound is converted to 0.05 to 5000 μg, preferably 0.1 to 0.5 μg, based on Fe.
1 to 3000 μg, more preferably 0.1 to 2000 μ
g, most preferably 0.3-1000 μg.
If the amount of the iron compound is less than the above range or, conversely, the amount thereof is more, the photocatalytic function tends to decrease.
【０００７】酸化チタン粒子の内部および／またはその
表面に鉄化合物を含有させると、光触媒機能が著しく向
上する理由については明らかでないが、酸化チタンの光
励起により生じた電子が鉄化合物に移行しやすいため、
正孔との電荷分離が容易になって、光触媒反応に関与す
る正孔や電子の量が増えたためと推察される。このこと
から、鉄化合物としては電子が移行しやすい三価の鉄化
合物が好ましく、また、酸化チタン粒子の表面に鉄化合
物が存在しているものが好ましいと考えられる。三価の
鉄化合物は酸化チタンの光励起により生じた電子を受け
取り二価の状態になるが、鉄原子のフェントン反応によ
り三価の状態に戻り、改めて電子を受け取ることができ
ると推測されている。The reason why the photocatalytic function is remarkably improved when an iron compound is contained inside and / or on the surface of the titanium oxide particles is not clear. However, since electrons generated by photoexcitation of titanium oxide easily migrate to the iron compound. ,
It is presumed that charge separation from holes was facilitated and the amount of holes and electrons involved in the photocatalytic reaction increased. From this, it is considered that the iron compound is preferably a trivalent iron compound to which electrons are easily transferred, and a compound in which the iron compound is present on the surface of the titanium oxide particles is preferable. The trivalent iron compound receives electrons generated by the photoexcitation of titanium oxide and becomes a divalent state. However, it is speculated that the trivalent iron compound returns to the trivalent state by the Fenton reaction of iron atoms and can receive electrons again.
【０００８】本発明の鉄化合物を表面に担持した酸化チ
タン光触媒は種々の方法によって得ることができる。た
とえば、硫酸チタニル、硫酸チタン、塩化チタン、有
機チタン化合物などのチタン化合物を鉄化合物の存在下
に、必要に応じてさらに結晶種の存在下に、チタン化合
物を加水分解あるいは中和する方法、鉄化合物の溶液
に酸化チタン粒子あるいは酸化チタン粒子を担持した支
持体を浸漬する方法、酸化チタン粒子の懸濁液あるい
は酸化チタン粒子を担持した支持体を入れた液に鉄化合
物を添加し、鉄化合物を加水分解したり、中和したり、
酸化したりする方法などがあるが、これらの方法は、優
れた特性のものが得られるため好ましいものである。前
記の方法において、予め鉄化合物を含有した硫酸チタ
ニル、硫酸チタン、塩化チタンを用い、これを加水分解
あるいは中和し、得られた酸化チタンに硝酸、塩酸など
の一塩基酸を添加して解膠したり、更に、加圧下で水熱
処理したりして鉄化合物を含有した酸化チタンとするこ
ともできる。また、予め鉄化合物を含有した硫酸チタニ
ル、硫酸チタン、塩化チタンとしては、鉄化合物を含有
したチタン鉱石を蒸解して得られるものを用いることが
できる。更に、チタン化合物の加水分解は、チタン化合
物の水溶液の沸点温度以下で行うことが好ましい。前記
、、の方法に用いる鉄化合物としては、たとえ
ば、鉄の硫酸塩、塩化物、硝酸塩などの水可溶性鉄化合
物が好ましい。また、中和に用いるアルカリとしては、
たとえば、水酸化ナトリウム、水酸化カリウム、炭酸ア
ンモニウム、アンモニア、アミン類など種々のアルカリ
が挙げられる。The titanium oxide photocatalyst carrying the iron compound of the present invention on the surface can be obtained by various methods. For example, a method of hydrolyzing or neutralizing a titanium compound such as titanyl sulfate, titanium sulfate, titanium chloride, and an organic titanium compound in the presence of an iron compound and, if necessary, in the presence of a crystal seed, A method of immersing a support supporting titanium oxide particles or titanium oxide particles in a solution of a compound, adding an iron compound to a suspension of titanium oxide particles or a liquid containing a support supporting titanium oxide particles, Hydrolyze or neutralize,
There are methods such as oxidation, and these methods are preferable because excellent characteristics can be obtained. In the above-mentioned method, titanyl sulfate, titanium sulfate, and titanium chloride containing an iron compound in advance are used, hydrolyzed or neutralized, and the obtained titanium oxide is decomposed by adding a monobasic acid such as nitric acid or hydrochloric acid. Titanium oxide containing an iron compound can also be obtained by agglutination or further hydrothermal treatment under pressure. As the titanyl sulfate, titanium sulfate, and titanium chloride containing the iron compound in advance, those obtained by digesting a titanium ore containing the iron compound can be used. Further, the hydrolysis of the titanium compound is preferably performed at a temperature not higher than the boiling point of the aqueous solution of the titanium compound. As the iron compound used in the above method, for example, a water-soluble iron compound such as an iron sulfate, chloride, or nitrate is preferable. Further, as the alkali used for neutralization,
For example, various alkalis such as sodium hydroxide, potassium hydroxide, ammonium carbonate, ammonia and amines can be mentioned.
【０００９】前記、の方法において用いる酸化チタ
ン粒子は種々の公知の方法で得ることができる。その方
法としては、たとえば、（ｉ）硫酸チタニル、硫酸チタ
ン、塩化チタン、有機チタン化合物などのチタン化合物
を、必要に応じて結晶種の存在下に、加水分解する方
法、（ｉｉ）硫酸チタニル、硫酸チタン、塩化チタン、
有機チタン化合物などのチタン化合物に、必要に応じて
結晶種の存在下に、アルカリを添加し、中和する方法、
（ｉｉｉ）塩化チタン、有機チタン化合物などを気相酸
化する方法、（ｉｖ）前記（ｉ）、（ｉｉ）、（ｉｉ
ｉ）の方法で得た酸化チタンを焼成、あるいは、酸化チ
タンの懸濁液を、必要に応じて酸またはアルカリを加
え、水熱処理する方法などがあり、前記（ｉ）、（ｉ
ｉ）の方法で得られた酸化チタンや（ｉｖ）の水熱処理
を施して得られた酸化チタンを用いると優れた光触媒機
能を有する酸化チタン光触媒が得られるため好ましい。
前記（ｉ）の方法において、チタン化合物の加水分解
は、チタン化合物の水溶液の沸点温度以下で行うことが
好ましい。The titanium oxide particles used in the above method can be obtained by various known methods. As the method, for example, (i) a method of hydrolyzing a titanium compound such as titanyl sulfate, titanium sulfate, titanium chloride, or an organic titanium compound in the presence of a crystal seed as necessary, (ii) titanyl sulfate, Titanium sulfate, titanium chloride,
A method of neutralizing by adding an alkali to a titanium compound such as an organic titanium compound, if necessary, in the presence of a crystal seed,
(Iii) a method of vapor-phase oxidation of titanium chloride, an organotitanium compound, or the like; (iv) the above (i), (ii), (ii)
There is a method of calcining the titanium oxide obtained by the method of i) or hydrotreating the titanium oxide suspension by adding an acid or an alkali, if necessary.
It is preferable to use the titanium oxide obtained by the method (i) or the titanium oxide obtained by performing the hydrothermal treatment of (iv) because a titanium oxide photocatalyst having an excellent photocatalytic function can be obtained.
In the method (i), the hydrolysis of the titanium compound is preferably performed at a temperature equal to or lower than the boiling point of the aqueous solution of the titanium compound.
【００１０】前記の方法において得られた生成物を本発
明の鉄化合物を含有した酸化チタン光触媒として用いる
ことができるが、必要に応じて、該生成物を分別し、洗
浄し、乾燥あるいは焼成してもよい。分別は通常の濾過
や傾斜法などの方法によって行うことができる。乾燥は
任意の温度で行うことができるが、１００〜２００℃の
温度が適当である。焼成の温度は２００〜５００℃の温
度が適当であり、この焼成により、鉄化合物が拡散して
酸化チタン粒子の内部に取り込まれやすい。なお、本発
明の方法においては、鉄化合物、チタン化合物、アルカ
リなどの濃度および添加速度、加水分解反応や中和反応
の温度、分散液中の酸化チタンの濃度などの条件は、特
に制限がなく適宜設定することができる。また、前記酸
化チタンの分散液に、オルソリン酸、ピロリン酸、ヘキ
サメタリン酸またはこれらのアルカリ塩、オルソケイ酸
ナトリウム、メタケイ酸ナトリウムなどの分散剤を光触
媒機能に悪影響を及ぼさない範囲の量添加することが可
能であり、分散剤の添加によって光触媒機能を向上させ
ることができる場合もある。The product obtained in the above method can be used as a titanium oxide photocatalyst containing the iron compound of the present invention. If necessary, the product is separated, washed, dried or calcined. You may. Separation can be performed by a conventional method such as filtration or a gradient method. Drying can be performed at any temperature, but a temperature of 100 to 200 ° C. is appropriate. The firing temperature is suitably from 200 to 500 ° C., and the firing facilitates the diffusion of the iron compound into the titanium oxide particles. In the method of the present invention, the conditions such as the concentration and addition rate of the iron compound, the titanium compound and the alkali, the temperature of the hydrolysis reaction and the neutralization reaction, and the concentration of the titanium oxide in the dispersion are not particularly limited. It can be set appropriately. Further, a dispersant such as orthophosphoric acid, pyrophosphoric acid, hexametaphosphoric acid or an alkali salt thereof, sodium orthosilicate, sodium metasilicate, or the like may be added to the titanium oxide dispersion in an amount that does not adversely affect the photocatalytic function. It is possible, and in some cases, the photocatalytic function can be improved by adding a dispersant.
【００１１】本発明は、酸化チタンを鉱酸処理してなる
酸化チタン光触媒に関する。本発明において、酸化チタ
ンとはアナタース型酸化チタン、ルチル型酸化チタン、
無定形酸化チタン、メタチタン酸、オルソチタン酸など
の各種の酸化チタンあるいは水酸化チタン、含水酸化チ
タン、水和酸化チタンを意味する。本発明においては、
アナタース型酸化チタンが優れた光触媒機能を有するた
め好ましい。酸化チタンの凝集体の平均粒子径は、好ま
しくは１〜１０００ｎｍ、より好ましくは５〜５００ｎ
ｍ、もっとも好ましくは５〜３００ｎｍである。前記の
酸化チタンは種々の方法によって得ることができる。そ
の方法としては、たとえば、前記の（ｉ）、（ｉｉ）、
（ｉｉｉ）、（ｉｖ）の方法などがあり、前記（ｉ）、
（ｉｉ）の方法で得られた酸化チタンや（ｉｖ）の水熱
処理を施して得られた酸化チタンを用いると優れた光触
媒機能を有する酸化チタン光触媒が得られるため好まし
い。更に、前記（ｉ）の方法において、チタン化合物の
加水分解は、チタン化合物の水溶液の沸点温度以下で行
うことが好ましい。このようにして得た酸化チタンを、
必要に応じて、液から分別したり、洗浄したり、乾燥し
たりしてもよい。The present invention relates to a titanium oxide photocatalyst obtained by treating titanium oxide with a mineral acid. In the present invention, titanium oxide is an anatase type titanium oxide, a rutile type titanium oxide,
It means various titanium oxides such as amorphous titanium oxide, metatitanic acid and orthotitanic acid, or titanium hydroxide, hydrous titanium oxide and hydrated titanium oxide. In the present invention,
Anatase-type titanium oxide is preferred because it has an excellent photocatalytic function. The average particle diameter of the aggregate of titanium oxide is preferably 1 to 1000 nm, more preferably 5 to 500 n.
m, most preferably from 5 to 300 nm. The above-mentioned titanium oxide can be obtained by various methods. As the method, for example, the above (i), (ii),
(Iii) and (iv).
It is preferable to use titanium oxide obtained by the method (ii) or titanium oxide obtained by performing the hydrothermal treatment of (iv), since a titanium oxide photocatalyst having an excellent photocatalytic function can be obtained. Further, in the method (i), the hydrolysis of the titanium compound is preferably performed at a temperature not higher than the boiling point of the aqueous solution of the titanium compound. The titanium oxide thus obtained is
If necessary, it may be separated from the liquid, washed, or dried.
【００１２】本発明において、酸化チタンを鉱酸で処理
するには、まず、酸化チタンの懸濁液に鉱酸を添加する
などして、該酸化チタンと鉱酸とを接触させる。次い
で、鉱酸と接触させた酸化チタンを液から分別し、必要
に応じて、洗浄し、乾燥あるいは焼成してもよい。分別
は通常の濾過や傾斜法などの方法によって行うことがで
きる。乾燥は任意の温度で行うことができるが、１００
〜２００℃の温度が適当である。焼成の温度は２００〜
５００℃の温度が適当である。前記の鉱酸としては、た
とえば、硫酸、塩酸、硝酸、フッ酸を挙げることがで
き、これらの鉱酸の一種または二種以上を用いることが
できる。本発明においては、フッ酸が好ましい。処理時
の鉱酸の濃度は好ましくは０．０００５〜２０規定、よ
り好ましくは０．００１〜１０規定、さらに好ましくは
０．０１〜５規定、もっとも好ましくは０．１〜２規定
である。前記の鉱酸の濃度が０．０００５規定より小さ
いと所望の効果が得られ難いため好ましくなく、また、
鉱酸の濃度が２０規定より大きいと酸化チタンの溶解が
進み過ぎるため好ましくない。鉱酸処理時の温度は適宜
設定できるが、０〜１００℃の温度、好ましくは室温〜
８０℃の温度、より好ましくは室温〜６０℃の温度であ
る。また、鉱酸処理の時間は適宜設定できるが、０．１
〜４８時間、好ましくは０．５〜１２時間、より好まし
くは０．５〜５時間である。このようにして、本発明の
鉱酸処理した酸化チタン光触媒が得られる。In the present invention, in order to treat titanium oxide with a mineral acid, the titanium oxide is first brought into contact with a mineral acid by, for example, adding a mineral acid to a suspension of the titanium oxide. Next, the titanium oxide that has been brought into contact with the mineral acid may be separated from the liquid, and, if necessary, washed, dried or fired. Separation can be performed by a conventional method such as filtration or a gradient method. Drying can be performed at any temperature,
Temperatures of ~ 200 ° C are suitable. The firing temperature is 200 ~
A temperature of 500 ° C. is suitable. Examples of the mineral acid include sulfuric acid, hydrochloric acid, nitric acid, and hydrofluoric acid, and one or more of these mineral acids can be used. In the present invention, hydrofluoric acid is preferred. The concentration of the mineral acid at the time of the treatment is preferably 0.0005 to 20 normal, more preferably 0.001 to 10 normal, further preferably 0.01 to 5 normal, and most preferably 0.1 to 2 normal. If the concentration of the mineral acid is less than 0.0005 normal, it is difficult to obtain the desired effect, which is not preferable.
If the concentration of the mineral acid is more than 20 normal, the dissolution of titanium oxide proceeds too much, which is not preferable. The temperature at the time of the mineral acid treatment can be appropriately set, but the temperature is 0 to 100 ° C, preferably room temperature to
A temperature of 80 ° C, more preferably a temperature of room temperature to 60 ° C. The time of the mineral acid treatment can be set as appropriate,
-48 hours, preferably 0.5-12 hours, more preferably 0.5-5 hours. Thus, the titanium oxide photocatalyst treated with the mineral acid of the present invention is obtained.
【００１３】次の本発明は、前記の鉱酸処理を施した酸
化チタン粒子の内部および／またはその表面に鉄化合物
を含有してなる酸化チタン光触媒に関する。本発明にお
いて、鉄化合物は、前記した鉄化合物、すなわち、酸化
鉄、水酸化鉄、オキシ水酸化鉄のほか、硫酸鉄、塩化
鉄、硝酸鉄、炭酸鉄、酢酸鉄などの鉄塩や鉄イオンを用
いることができる。本発明においては、三価および／ま
たは二価の鉄の化合物が一般的であり、酸化チタンの光
触媒機能を向上させるうえから好ましく、たとえば、酸
化鉄（Ｆｅ2 Ｏ3 、Ｆｅ3 Ｏ4 ）、水酸化鉄（Ｆｅ（Ｏ
Ｈ）2 、Ｆｅ（ＯＨ）3 ）、オキシ水酸化鉄（ＦｅＯＯ
Ｈ）が好ましいものである。鉄化合物の含有量は、対象
とする光触媒反応により任意に変えられるが、酸化チタ
ンのＴｉＯ2 重量基準に対して、鉄化合物をＦｅ基準に
換算して０．０００５〜１０重量％、好ましくは０．０
０１〜５重量％、より好ましくは０．００１〜３重量
％、もっとも好ましくは０．００１〜１重量％である。
鉄化合物が前記範囲より少なかったり、また逆に多かっ
たりすると光触媒機能が低下する傾向にある。本発明に
おいては、酸化チタン光触媒に含まれる鉄化合物は、酸
化チタン粒子の表面に担持されている状態が好ましく、
この場合の鉄化合物の担持量は酸化チタン粒子の表面積
１ｍ2 当たり、鉄化合物をＦｅ基準に換算して０．０５
〜５０００μｇ、好ましくは０．１〜３０００μｇ、よ
り好ましくは０．１〜２０００μｇ、もっとも好ましく
は０．３〜１０００μｇである。鉄化合物が前記範囲よ
り少なかったり、また逆に多かったりすると光触媒機能
が低下する傾向にある。The present invention relates to a titanium oxide photocatalyst containing an iron compound inside and / or on the surface of the above-mentioned mineral oxide-treated titanium oxide particles. In the present invention, the iron compound is the above-mentioned iron compound, that is, iron oxide, iron hydroxide, iron oxyhydroxide, iron sulfate, iron chloride, iron nitrate, iron carbonate, iron acetate such as iron acetate and iron ion Can be used. In the present invention, trivalent and / or divalent iron compounds are generally used, and are preferable from the viewpoint of improving the photocatalytic function of titanium oxide. For example, iron oxides (Fe 2 O 3 , Fe 3 O 4 ), Iron hydroxide (Fe (O
H) 2 , Fe (OH) 3 ), iron oxyhydroxide (FeOO)
H) is preferred. The content of the iron compound can be arbitrarily changed depending on the target photocatalytic reaction. However, the content of the iron compound is 0.0005 to 10% by weight, preferably 0 to 10% by weight, based on the TiO 2 weight of titanium oxide. .0
It is from 0.01 to 5% by weight, more preferably from 0.001 to 3% by weight, most preferably from 0.001 to 1% by weight.
If the amount of the iron compound is less than the above range or, conversely, the amount thereof is more, the photocatalytic function tends to decrease. In the present invention, the iron compound contained in the titanium oxide photocatalyst is preferably supported on the surface of the titanium oxide particles,
In this case, the supported amount of the iron compound was 0.05 per unit area of 1 m 2 of the titanium oxide particles in terms of Fe compound.
5,000 μg, preferably 0.1-3000 μg, more preferably 0.1-2000 μg, most preferably 0.3-1000 μg. If the amount of the iron compound is less than the above range or, conversely, the amount thereof is more, the photocatalytic function tends to decrease.
【００１４】本発明の鉄化合物を表面に担持した酸化チ
タン光触媒を得るには、（ａ）鉱酸処理を施した酸化チ
タンを含有した鉱酸処理液、または、鉱酸処理を施した
酸化チタンあるいは鉱酸処理を施した酸化チタンを保持
した支持体を懸濁した液に、鉄化合物を添加する方法、
（ｂ）前記（ａ）の鉄化合物の添加の後に、該鉄化合物
を中和したり、加水分解したり、酸化したりする方法、
（ｃ）鉄化合物の溶液に、鉱酸処理を施した酸化チタ
ン、または、鉱酸処理を施した酸化チタンを保持した支
持体を浸漬する方法、（ｄ）前記（ｃ）の浸漬の後に、
鉄化合物を中和したり、加水分解したり、酸化したりす
る方法などを用いることができる。前記（ａ）、
（ｂ）、（ｃ）、（ｄ）の方法に用いる鉄化合物として
は、たとえば、鉄の硫酸塩、塩化物、硝酸塩などの水可
溶性鉄化合物が好ましい。また、中和に用いるアルカリ
としては、たとえば、水酸化ナトリウム、水酸化カリウ
ム、炭酸アンモニウム、アンモニア、アミン類などの種
々のアルカリが挙げられる。このようにして得られた生
成物を本発明の鉄化合物を含有した酸化チタン光触媒と
して用いることができるが、必要に応じて、該生成物を
分別し、洗浄し、乾燥あるいは焼成してもよい。分別は
通常の濾過や傾斜法などの方法によって行うことができ
る。乾燥は任意の温度で行うことができるが、１００〜
２００℃の温度が適当である。焼成の温度は２００〜５
００℃の温度が適当であり、この焼成により、鉄化合物
が拡散して酸化チタン粒子の内部に取り込まれやすい。
このようにして、本発明の鉱酸処理を施した酸化チタン
粒子の内部および／またはその表面に鉄化合物を含有し
てなる酸化チタン光触媒が得られる。In order to obtain a titanium oxide photocatalyst having the iron compound of the present invention supported on its surface, (a) a mineral acid treatment solution containing a mineral acid treated titanium oxide or a mineral acid treated titanium oxide Alternatively, a method of adding an iron compound to a suspension of a support holding titanium oxide subjected to a mineral acid treatment,
(B) a method of neutralizing, hydrolyzing, or oxidizing the iron compound after the addition of the iron compound of (a);
(C) a method of immersing a titanium oxide treated with a mineral acid or a support holding the titanium oxide treated with a mineral acid in a solution of an iron compound, (d) after immersion in the above (c),
A method of neutralizing, hydrolyzing, or oxidizing an iron compound can be used. (A),
As the iron compound used in the methods (b), (c) and (d), for example, water-soluble iron compounds such as iron sulfate, chloride and nitrate are preferable. Examples of the alkali used for neutralization include various alkalis such as sodium hydroxide, potassium hydroxide, ammonium carbonate, ammonia, and amines. The product obtained in this way can be used as a titanium oxide photocatalyst containing the iron compound of the present invention, but if necessary, the product may be separated, washed, dried or calcined. . Separation can be performed by a conventional method such as filtration or a gradient method. Drying can be performed at any temperature,
A temperature of 200 ° C. is suitable. Firing temperature is 200-5
A temperature of 00 ° C. is appropriate, and the firing facilitates the diffusion of the iron compound into the titanium oxide particles.
Thus, a titanium oxide photocatalyst containing an iron compound inside and / or on the surface of the titanium oxide particles subjected to the mineral acid treatment of the present invention is obtained.
【００１５】本発明の酸化チタン光触媒を、有機物質の
合成反応や有害物質の分解反応などの種々の光触媒反応
に用いるには、処理対象物質の存在下、該酸化チタン光
触媒にそのバンドギャップ以上のエネルギーを持つ波長
の光を照射する。本発明の酸化チタン光触媒は、使用場
面に応じて、溶媒に懸濁した状態、支持体に保持あるい
は被覆した状態、該酸化チタン光触媒を粉末の状態、あ
るいは該粉末を粉砕した状態、さらには、該粉末を成形
した状態で用いることもできる。酸化チタンの光触媒反
応により分解あるいは酸化して除去する有害物質として
は、人体や生活環境に悪影響を及ぼす物質やその可能性
がある物質であり、たとえば、種々の生物学的酸素要求
物質、大気汚染物質などの環境汚染物質や除草剤、殺菌
剤、殺虫剤、殺線虫剤などの種々の農薬などの物質、細
菌、放線菌、菌類、藻類、カビ類などの微生物などが挙
げられる。環境汚染物質としては、有機ハロゲン化合
物、有機リン化合物やそれ以外の有機化合物、窒素化合
物、硫黄化合物、シアン化合物、クロム化合物などの無
機化合物が挙げられる。有機ハロゲン化合物としては、
具体的には、ポリ塩化ビフェニル、フロン、トリハロメ
タン、トリクロロエチレン、テトラクロロエチレンが例
示できる。有機ハロゲン化合物、有機リン化合物以外の
有機物質としては、具体的には、界面活性剤や油類など
の炭化水素類、アルデヒド類、メルカプタン類、アルコ
ール類、アミン類、アミノ酸、蛋白質が例示できる。ま
た、窒素化合物としては、具体的には、アンモニア、窒
素酸化物が例示できる。バンドギャップ以上のエネルギ
ーを持つ波長の光としては、紫外線を含有した光が好ま
しく、たとえば、太陽光や蛍光灯、ブラックライト、ハ
ロゲンランプ、キセノンフラッシュランプ、水銀灯など
の光を用いることができる。特に３００〜４００ｎｍの
近紫外線を含有した光が好ましい。光の照射量や照射時
間などは処理対象物質の量などによって適宜設定でき
る。In order to use the titanium oxide photocatalyst of the present invention in various photocatalytic reactions such as a synthesis reaction of an organic substance and a decomposition reaction of a harmful substance, the titanium oxide photocatalyst is required to have a band gap equal to or larger than its band gap in the presence of the substance to be treated. Irradiates light with a wavelength having energy. The titanium oxide photocatalyst of the present invention is in a state of being suspended in a solvent, a state of being held or coated on a support, a state of the titanium oxide photocatalyst in a powder state, or a state in which the powder is pulverized, The powder can be used in a molded state. Hazardous substances that are decomposed or oxidized and removed by the photocatalytic reaction of titanium oxide include substances that have a negative effect on the human body and living environment, and substances that have the potential for such harmful substances. For example, various biological oxygen demanding substances, air pollution Examples include environmental pollutants such as substances, substances such as various pesticides such as herbicides, fungicides, insecticides, nematicides, and microorganisms such as bacteria, actinomycetes, fungi, algae, and molds. Examples of the environmental pollutants include organic halogen compounds, organic phosphorus compounds and other organic compounds, and inorganic compounds such as nitrogen compounds, sulfur compounds, cyanide compounds, and chromium compounds. As organic halogen compounds,
Specific examples include polychlorinated biphenyl, freon, trihalomethane, trichloroethylene, and tetrachloroethylene. Specific examples of the organic substance other than the organic halogen compound and the organic phosphorus compound include hydrocarbons such as surfactants and oils, aldehydes, mercaptans, alcohols, amines, amino acids, and proteins. In addition, specific examples of the nitrogen compound include ammonia and nitrogen oxides. As the light having a wavelength having energy equal to or greater than the band gap, light containing ultraviolet light is preferable, and for example, light such as sunlight, a fluorescent lamp, a black light, a halogen lamp, a xenon flash lamp, and a mercury lamp can be used. Particularly, light containing near-ultraviolet light of 300 to 400 nm is preferable. The light irradiation amount and irradiation time can be appropriately set depending on the amount of the substance to be treated.
【００１６】[0016]
実施例１ ８０ｇ／ｌの硫酸チタニルの水溶液１リットルを８５℃
の温度に加熱し３時間保持して、硫酸チタニルを加水分
解した。このようにして得られた加水分解生成物を濾過
し、洗浄した後、水に懸濁させ、ＴｉＯ2 に換算して５
０ｇ／ｌの懸濁液とした。次いで、前記の懸濁液に硝酸
水溶液を添加して液のｐＨを１．０に調整した後、該懸
濁液をオートクレーブに入れ、飽和蒸気圧下、１８０℃
の温度で１３時間水熱処理した。この後、得られた生成
物を濾過し、洗浄し、乾燥して、酸化チタン（試料１）
を得た。なお、試料１の比表面積は８０．４ｍ2 ／ｇで
あり、アナタース型結晶を有しており、Ｓｃｈｅｒｒｅ
ｒの式から求めた平均粒子径は１７．０ｎｍであった。
前記の試料１の酸化チタン１０ｇを、塩化鉄（ＦｅＣｌ
3 ・６Ｈ2 Ｏ）１．４５ｍｇを溶解した酸性水溶液に浸
漬し、次いで、蒸発乾固して乾燥した。得られた乾燥物
を粉砕した後、水に懸濁させ、ＴｉＯ2 に換算して１０
０ｇ／ｌの懸濁液とし、次いで該懸濁液にアンモニア水
を添加して液のｐＨを７．０に調整した後、濾過し、洗
浄し、乾燥して、本発明の鉄化合物を含有した酸化チタ
ン光触媒（試料Ａ）を得た。この試料Ａは、酸化チタン
のＴｉＯ2 重量基準に対して、Ｆｅ基準に換算して０．
００２９重量％の水酸化鉄を含有しており、酸化チタン
粒子の表面積１ｍ2 当たりの水酸化鉄の担持量はＦｅ基
準に換算して０．３６μｇであった。Example 1 One liter of an aqueous solution of 80 g / l titanyl sulfate was heated to 85 ° C.
And heated for 3 hours to hydrolyze titanyl sulfate. The hydrolysis product thus obtained is filtered, washed, suspended in water, and converted to TiO 2 by 5%.
A suspension of 0 g / l was obtained. Next, an aqueous solution of nitric acid was added to the suspension to adjust the pH of the solution to 1.0, and then the suspension was placed in an autoclave and heated at 180 ° C under a saturated vapor pressure.
For 13 hours. Thereafter, the obtained product is filtered, washed and dried, and titanium oxide (sample 1)
I got The specific surface area of Sample 1 was 80.4 m 2 / g, and had an anatase crystal.
The average particle diameter determined from the equation for r was 17.0 nm.
10 g of the titanium oxide of the above-mentioned sample 1 was added to iron chloride
3 · 6H 2 O) 1.45mg immersed in an acidic aqueous solution of, then dried and evaporated to dryness. The obtained dried product is pulverized, suspended in water, and converted to TiO 2 by 10%.
The suspension was adjusted to pH 7.0 by adding aqueous ammonia to the suspension, and then filtered, washed, and dried to contain the iron compound of the present invention. The obtained titanium oxide photocatalyst (sample A) was obtained. This sample A was converted to Fe standard on the basis of TiO 2 weight basis of titanium oxide.
It contained 0029% by weight of iron hydroxide, and the amount of iron hydroxide supported per 1 m 2 of surface area of the titanium oxide particles was 0.36 μg in terms of Fe standard.
【００１７】実施例２ 実施例１において、塩化鉄（ＦｅＣｌ3 ・６Ｈ2 Ｏ）
４．８３ｍｇを溶解した酸性水溶液を用いたこと以外
は、実施例１と同様に処理して、本発明の鉄化合物を含
有した酸化チタン光触媒（試料Ｂ）を得た。この試料Ｂ
は、酸化チタンのＴｉＯ2 重量基準に対して、Ｆｅ基準
に換算して０．０１０重量％の水酸化鉄を含有してお
り、酸化チタン粒子の表面積１ｍ2 当たりの水酸化鉄の
担持量はＦｅ基準に換算して１．２μｇであった。Example 2 In Example 1, iron chloride (FeCl 3 .6H 2 O) was used.
A titanium oxide photocatalyst containing the iron compound of the present invention (sample B) was obtained in the same manner as in Example 1, except that an acidic aqueous solution in which 4.83 mg was dissolved was used. This sample B
Contains 0.010% by weight of iron hydroxide in terms of Fe based on the TiO 2 weight of titanium oxide, and the amount of iron hydroxide supported per 1 m 2 of surface area of the titanium oxide particles is It was 1.2 μg in terms of Fe standard.
【００１８】実施例３ 実施例１において、塩化鉄（ＦｅＣｌ3 ・６Ｈ2 Ｏ）
８．７０ｍｇを溶解した酸性水溶液を用いたこと以外
は、実施例１と同様に処理して、本発明の鉄化合物を含
有した酸化チタン光触媒（試料Ｃ）を得た。この試料Ｃ
は、酸化チタンのＴｉＯ2 重量基準に対して、Ｆｅ基準
に換算して０．０１８重量％の水酸化鉄を含有してお
り、酸化チタン粒子の表面積１ｍ2 当たりの水酸化鉄の
担持量はＦｅ基準に換算して２．２μｇであった。Example 3 In Example 1, iron chloride (FeCl 3 .6H 2 O) was used.
A titanium oxide photocatalyst containing the iron compound of the present invention (sample C) was obtained in the same manner as in Example 1, except that an acidic aqueous solution in which 8.70 mg was dissolved was used. This sample C
Contains 0.018% by weight of iron hydroxide in terms of Fe based on the weight of TiO 2 of titanium oxide, and the amount of iron hydroxide supported per 1 m 2 of surface area of titanium oxide particles is It was 2.2 μg in terms of Fe standard.
【００１９】実施例４ 実施例１において、塩化鉄（ＦｅＣｌ3 ・６Ｈ2 Ｏ）１
４５ｍｇを溶解した酸性水溶液を用いたこと以外は、実
施例１と同様に処理して、本発明の鉄化合物を含有した
酸化チタン光触媒（試料Ｄ）を得た。この試料Ｄは、酸
化チタンのＴｉＯ2 重量基準に対して、Ｆｅ基準に換算
して０．３０重量％の水酸化鉄を含有しており、酸化チ
タン粒子の表面積１ｍ2 当たりの水酸化鉄の担持量はＦ
ｅ基準に換算して３７μｇであった。Example 4 In Example 1, iron chloride (FeCl 3 .6H 2 O) 1
A titanium oxide photocatalyst containing the iron compound of the present invention (sample D) was obtained in the same manner as in Example 1 except that an acidic aqueous solution in which 45 mg was dissolved was used. This sample D contains 0.30% by weight of iron hydroxide in terms of Fe based on the weight of TiO 2 of titanium oxide, and the amount of iron hydroxide per 1 m 2 of surface area of titanium oxide particles. Loading amount is F
It was 37 μg in terms of e standard.
【００２０】比較例１ 実施例１において得られた試料１の酸化チタンを比較試
料Ｅとして用いた。なお、この試料１は、酸化チタンの
ＴｉＯ2 重量基準に対して、Ｆｅ基準に換算して０．０
００１重量％の鉄化合物を含有していた。Comparative Example 1 The titanium oxide of Sample 1 obtained in Example 1 was used as Comparative Sample E. In addition, this sample 1 was 0.0% in terms of Fe based on the TiO 2 weight basis of titanium oxide.
It contained 001% by weight of iron compound.
【００２１】実施例５ 実施例１において、試料１の酸化チタンを５００℃の温
度で２時間焼成して得た酸化チタン（試料２）を試料１
に代えて用いたこと、塩化鉄（ＦｅＣｌ3 ・６Ｈ2 Ｏ）
１４．５ｍｇを溶解した酸性水溶液を用いたこと以外
は、実施例１と同様に処理して、本発明の鉄化合物を含
有した酸化チタン光触媒（試料Ｆ）を得た。この試料Ｆ
は、酸化チタンのＴｉＯ2 重量基準に対して、Ｆｅ基準
に換算して０．０２９重量％の水酸化鉄を含有してお
り、酸化チタン粒子の表面積１ｍ2 当たりの水酸化鉄の
担持量はＦｅ基準に換算して５．９μｇであった。な
お、試料２の酸化チタンの比表面積は４９．４ｍ2 ／ｇ
であり、アナタース型結晶を有しており、Ｓｃｈｅｒｒ
ｅｒの式から求めた平均粒子径は１８．２ｎｍであっ
た。Example 5 In Example 1, titanium oxide (Sample 2) obtained by calcining the titanium oxide of Sample 1 at a temperature of 500 ° C. for 2 hours was used.
Place of that used in the iron chloride (FeCl 3 · 6H 2 O)
A titanium oxide photocatalyst containing the iron compound of the present invention (sample F) was obtained in the same manner as in Example 1, except that an acidic aqueous solution in which 14.5 mg was dissolved was used. This sample F
Contains 0.029% by weight of iron hydroxide in terms of Fe based on the TiO 2 weight of titanium oxide, and the amount of iron hydroxide supported per 1 m 2 of surface area of the titanium oxide particles is It was 5.9 μg in terms of Fe standard. The specific surface area of the titanium oxide of Sample 2 was 49.4 m 2 / g.
And having an anatase-type crystal, Scherr
The average particle size determined from the equation of er was 18.2 nm.
【００２２】実施例６ 実施例５に記載の試料２の酸化チタン１０ｇを水に懸濁
させ、ＴｉＯ2 に換算して１００ｇ／ｌの懸濁液とし
た。次いで、前記の懸濁液に攪拌下、塩化鉄（ＦｅＣｌ
3 ・６Ｈ2 Ｏ）１４．５ｍｇを溶解した酸性水溶液を添
加した後、アンモニア水を添加して液のｐＨを７．０に
調整し、次いで、濾過し、洗浄し、乾燥して、本発明の
鉄化合物を含有した酸化チタン光触媒（試料Ｇ）を得
た。この試料Ｇは、酸化チタンのＴｉＯ2 重量基準に対
して、Ｆｅ基準に換算して０．０２９重量％の水酸化鉄
を含有しており、酸化チタン粒子の表面積１ｍ2 当たり
の水酸化鉄の担持量はＦｅ基準に換算して５．９μｇで
あった。Example 6 10 g of the titanium oxide of Sample 2 described in Example 5 was suspended in water to obtain a suspension of 100 g / l in terms of TiO 2 . Next, iron chloride (FeCl 2) was added to the suspension while stirring.
3 · 6H 2 O) was added an acidic aqueous solution containing 14.5 mg, the pH of the solution was adjusted to 7.0 by adding aqueous ammonia, then filtered, washed, and dried, the present invention A titanium oxide photocatalyst containing the iron compound (Sample G) was obtained. This sample G contains 0.029% by weight of iron hydroxide in terms of Fe based on the TiO 2 weight of titanium oxide, and the amount of iron hydroxide per 1 m 2 of the surface area of titanium oxide particles. The supported amount was 5.9 μg in terms of Fe standard.
【００２３】実施例７ 実施例６で得られた試料Ｇを３００℃の温度で１時間焼
成して、本発明の鉄化合物を含有した酸化チタン光触媒
（試料Ｈ）を得た。この試料Ｈは、酸化チタンのＴｉＯ
2 重量基準に対して、Ｆｅ基準に換算して０．０２９重
量％の水酸化鉄を含有していた。Example 7 Sample G obtained in Example 6 was calcined at a temperature of 300 ° C. for 1 hour to obtain a titanium oxide photocatalyst containing the iron compound of the present invention (Sample H). This sample H is made of titanium oxide TiO.
It contained 0.029% by weight of iron hydroxide in terms of Fe based on 2 % by weight.
【００２４】実施例８ 塩化鉄（ＦｅＣｌ3 ・６Ｈ2 Ｏ）１４．５ｍｇを溶解し
た酸性水溶液に、実施例５に記載の試料２の酸化チタン
１０ｇを浸漬した後、濾過し、洗浄し、乾燥して、本発
明の鉄化合物を含有した酸化チタン光触媒（試料Ｉ）を
得た。この試料Ｉは、酸化チタンのＴｉＯ2 重量基準に
対して、Ｆｅ基準に換算して０．０２９重量％の鉄化合
物を含有しており、酸化チタン粒子の表面積１ｍ2 当た
りの鉄化合物の担持量はＦｅ基準に換算して５．９μｇ
であった。Example 8 10 g of the titanium oxide of Sample 2 described in Example 5 was immersed in an acidic aqueous solution in which 14.5 mg of iron chloride (FeCl 3 .6H 2 O) was dissolved, followed by filtration, washing and drying. Thus, a titanium oxide photocatalyst containing the iron compound of the present invention (sample I) was obtained. This sample I contains 0.029% by weight of an iron compound in terms of Fe based on the TiO 2 weight of titanium oxide, and the amount of iron compound carried per 1 m 2 of surface area of the titanium oxide particles. Is 5.9 μg in terms of Fe standard
Met.
【００２５】比較例２ 実施例５において得られた試料２の酸化チタンを比較試
料Ｊとして用いた。なお、この試料２は、酸化チタンの
ＴｉＯ2 重量基準に対して、Ｆｅ基準に換算して０．０
００１重量％の鉄化合物を含有していた。Comparative Example 2 The titanium oxide of Sample 2 obtained in Example 5 was used as Comparative Sample J. Note that this sample 2 was converted to Fe-based with respect to TiO 2 weight-based
It contained 001% by weight of iron compound.
【００２６】実施例９ 実施例１において、試料１に代えて下記の試料３の酸化
チタンを用いたこと、塩化鉄（ＦｅＣｌ3 ・６Ｈ2 Ｏ）
１４．５ｍｇを溶解した酸性水溶液を用いたこと以外
は、実施例１と同様に処理して、本発明の鉄化合物を含
有した酸化チタン光触媒（試料Ｋ）を得た。この試料Ｋ
は、酸化チタンのＴｉＯ2 重量基準に対して、Ｆｅ基準
に換算して０．０２９重量％の水酸化鉄を含有してお
り、酸化チタン粒子の表面積１ｍ2 当たりの水酸化鉄の
担持量はＦｅ基準に換算して１．６μｇであった。な
お、試料３は次のようにして作製した。８０ｇ／ｌの四
塩化チタンの水溶液１リットルに、攪拌下、４モル／ｌ
のアンモニア水を滴下し、液のｐＨを７．０に調整して
四塩化チタンを室温で中和した。このようにして得られ
た中和生成物を濾過し、洗浄した後、水に懸濁させ、Ｔ
ｉＯ2 に換算して５０ｇ／ｌの懸濁液とした。次いで、
前記の懸濁液に硝酸水溶液を添加して液のｐＨを１．０
に調整し、ＴｉＯ2 に対してモル比で表して０．１の三
塩化チタンを添加した後、還流下、窒素ガスでバブリン
グしながら１００℃の温度で４時間加熱した。得られた
生成物を濾過し、洗浄し、乾燥して、酸化チタン（試料
３）を得た。なお、試料３の比表面積は１７６．６ｍ2
／ｇであり、アナタース型結晶を有しており、Ｓｃｈｅ
ｒｒｅｒの式から求めた平均粒子径は７．４ｎｍであっ
た。Example 9 In Example 1, titanium oxide of the following sample 3 was used in place of sample 1, and iron chloride (FeCl 3 .6H 2 O) was used.
A titanium oxide photocatalyst containing the iron compound of the present invention (sample K) was obtained in the same manner as in Example 1 except that an acidic aqueous solution in which 14.5 mg was dissolved was used. This sample K
Contains 0.029% by weight of iron hydroxide in terms of Fe based on the TiO 2 weight of titanium oxide, and the amount of iron hydroxide supported per 1 m 2 of surface area of the titanium oxide particles is It was 1.6 μg in terms of Fe standard. In addition, the sample 3 was produced as follows. To 1 liter of an aqueous solution of 80 g / l titanium tetrachloride, add 4 mol / l with stirring.
Was added dropwise, the pH of the solution was adjusted to 7.0, and titanium tetrachloride was neutralized at room temperature. The neutralized product thus obtained is filtered, washed and then suspended in water.
A suspension of 50 g / l in terms of iO 2 was obtained. Then
An aqueous nitric acid solution was added to the suspension to adjust the pH of the solution to 1.0.
After adding titanium trichloride in a molar ratio of 0.1 with respect to TiO 2 , the mixture was heated at 100 ° C. for 4 hours while bubbling with nitrogen gas under reflux. The obtained product was filtered, washed and dried to obtain titanium oxide (sample 3). The specific surface area of Sample 3 was 176.6 m 2.
/ G, having an anatase type crystal, and
The average particle diameter determined from the rrer equation was 7.4 nm.
【００２７】比較例３ 実施例９において得られた試料３の酸化チタンを比較試
料Ｌとして用いた。なお、この試料３は、酸化チタンの
ＴｉＯ2 重量基準に対して、Ｆｅ基準に換算して０．０
００１重量％の鉄化合物を含有していた。Comparative Example 3 The titanium oxide of Sample 3 obtained in Example 9 was used as Comparative Sample L. In addition, this sample 3 was 0.0% in terms of Fe based on the TiO 2 weight basis of titanium oxide.
It contained 001% by weight of iron compound.
【００２８】実施例１０ ８０ｇ／ｌの硫酸チタニルの水溶液１リットルに、硫酸
鉄（ＦｅＳＯ4 ・７Ｈ2 Ｏ）１２．１ｍｇを溶解した酸
性水溶液を添加した後、８５℃の温度に加熱し３時間保
持して、硫酸チタニルを加水分解した。このようにして
得られた加水分解生成物を濾過し、洗浄し、乾燥して、
本発明の鉄化合物を含有した酸化チタン光触媒（試料
Ｍ）を得た。この試料Ｍは、酸化チタンのＴｉＯ2 重量
基準に対して、Ｆｅ基準に換算して０．００６０重量％
の水酸化鉄を含有しており、比表面積は２９７．０ｍ2
／ｇであり、アナタース型結晶を有しており、Ｓｃｈｅ
ｒｒｅｒの式から求めた平均粒子径は７．０ｎｍであっ
た。The aqueous solution one liter of titanyl sulfate of Example 10 80 g / l, was added an acidic aqueous solution of iron sulfate (FeSO 4 · 7H 2 O) 12.1mg, 3 hours and heated to a temperature of 85 ° C. While holding, the titanyl sulfate was hydrolyzed. The hydrolysis product thus obtained is filtered, washed and dried,
A titanium oxide photocatalyst containing the iron compound of the present invention (sample M) was obtained. This sample M was 0.0060% by weight in terms of Fe based on the weight of TiO 2 of titanium oxide.
And a specific surface area of 297.0 m 2
/ G, having an anatase type crystal, and
The average particle diameter determined from the rrer equation was 7.0 nm.
【００２９】実施例および比較例で得られた試料（Ａ〜
Ｍ）の光触媒機能を以下のようにして調べた。各試料
０．１ｇをイオン交換水に分散させ、ＴｉＯ2 に換算し
て４ｇ／ｌの懸濁液とした。これらの懸濁液２５ｍｌに
２−プロパノール２５μｌを添加した後、ブラックライ
トを２時間照射して、２−プロパノールの光触媒反応を
行った。光量は２ｍＷ／ｃｍ2 であった。照射面積は２
８ｃｍ2 であった。反応中の２−プロパノールの濃度変
化を測定し、一次反応分解速度定数ｋを算出した。その
結果を表１に示す。この表から明らかなように、本発明
の鉄化合物を含有した酸化チタンは光触媒活性に優れて
いることがわかった。The samples obtained in Examples and Comparative Examples (A to
The photocatalytic function of M) was examined as follows. 0.1 g of each sample was dispersed in ion-exchanged water to obtain a suspension of 4 g / l in terms of TiO 2 . After adding 25 μl of 2-propanol to 25 ml of the suspension, the mixture was irradiated with black light for 2 hours to perform a photocatalytic reaction of 2-propanol. The light amount was 2 mW / cm 2 . Irradiation area is 2
8 cm 2 . The change in the concentration of 2-propanol during the reaction was measured, and the first-order decomposition rate constant k was calculated. Table 1 shows the results. As is clear from this table, it was found that the titanium oxide containing the iron compound of the present invention was excellent in photocatalytic activity.
【００３０】[0030]
【表１】 [Table 1]
【００３１】実施例１１ 実施例６において、試料２に代えて下記の試料４の酸化
チタンを用いたこと、塩化鉄（ＦｅＣｌ3 ・６Ｈ2 Ｏ）
１４５ｍｇを溶解した酸性水溶液を用いたこと以外は、
実施例６と同様に処理して、本発明の鉄化合物を含有し
た酸化チタン光触媒（試料Ｎ）を得た。この試料Ｎは、
酸化チタンのＴｉＯ2 重量基準に対して、Ｆｅ基準に換
算して０．２９重量％の水酸化鉄を含有しており、酸化
チタン粒子の表面積１ｍ2 当たりの水酸化鉄の担持量は
Ｆｅ基準に換算して４８μｇであった。なお、試料４は
次のようにして作製した。８０ｇ／ｌの硫酸チタニルの
水溶液１リットルを８５℃の温度に加熱し３時間保持し
て、硫酸チタニルを加水分解した。このようにして得ら
れた加水分解生成物を濾過し、洗浄した後、水に懸濁さ
せ、ＴｉＯ2 に換算して５０ｇ／ｌの懸濁液とした。次
いで、前記の懸濁液に硝酸水溶液を添加して液のｐＨを
１．０に調整した後、水酸化ナトリウムを加えて、ｐＨ
７．０に調整し、次いで、濾過し、洗浄した。得られた
酸化チタン湿ケーキに水を加え、ＴｉＯ2 に換算して１
００ｇ／ｌのスラリーを調製した。このスラリーに水酸
化ナトリウムを加えてｐＨ１０．０に調節した後、オー
トクレーブで１５０℃の温度で３時間水熱処理を行っ
た。次いで、水熱処理後のスラリーに硝酸を加えてｐＨ
７．０に中和した後、濾過し、洗浄し、乾燥して、酸化
チタン（試料４）を得た。なお、試料４の比表面積は６
０．０ｍ2 ／ｇであり、アナタース型結晶を有してお
り、Ｓｃｈｅｒｒｅｒの式から求めた平均粒子径は２
０．０ｎｍであった。Example 11 In Example 6, titanium oxide of the following sample 4 was used instead of sample 2, and iron chloride (FeCl 3 .6H 2 O) was used.
Except for using an acidic aqueous solution in which 145 mg was dissolved,
By treating in the same manner as in Example 6, a titanium oxide photocatalyst containing the iron compound of the present invention (sample N) was obtained. This sample N
It contains 0.29% by weight of iron hydroxide in terms of Fe based on the TiO 2 weight of titanium oxide. The amount of iron hydroxide supported per 1 m 2 of surface area of titanium oxide particles is based on Fe. It was 48 μg in terms of. In addition, the sample 4 was produced as follows. One liter of an aqueous solution of 80 g / l titanyl sulfate was heated to a temperature of 85 ° C. and held for 3 hours to hydrolyze titanyl sulfate. The hydrolysis product thus obtained was filtered, washed and suspended in water to obtain a suspension of 50 g / l in terms of TiO 2 . Next, an aqueous solution of nitric acid was added to the suspension to adjust the pH of the solution to 1.0, and then sodium hydroxide was added to the suspension to adjust the pH.
Adjusted to 7.0, then filtered and washed. Water is added to the obtained titanium oxide wet cake, and converted to TiO 2 to 1
A slurry of 00 g / l was prepared. The slurry was adjusted to pH 10.0 by adding sodium hydroxide, and then subjected to a hydrothermal treatment at 150 ° C. for 3 hours in an autoclave. Next, nitric acid was added to the slurry after the hydrothermal treatment to adjust the pH.
After neutralization to 7.0, the mixture was filtered, washed, and dried to obtain titanium oxide (sample 4). The specific surface area of sample 4 was 6
0.0 m 2 / g, having an anatase crystal, and having an average particle size of 2 as determined by Scherrer's equation.
0.0 nm.
【００３２】実施例１２ Ｆｅとして５４ｇ／ｌの硫酸鉄を含有する２１０ｇ／ｌ
の硫酸チタニル水溶液１リットルを８５℃の温度に加熱
し３時間保持して、硫酸チタニルを加水分解した後、硝
酸を添加して、液のｐＨを１．５に調整して解膠した。
次いで、この解膠した液に水酸化ナトリウムを加えて、
ｐＨ７．０に調整し、次いで、濾過し、洗浄し、乾燥し
て、本発明の鉄化合物を含有した酸化チタン光触媒（試
料Ｏ）を得た。この試料Ｏは、酸化チタンのＴｉＯ2 重
量基準に対して、Ｆｅ基準に換算して０．０２５重量％
の水酸化鉄を含有しており、酸化チタン粒子の表面積１
ｍ2 当たりの水酸化鉄の担持量はＦｅ基準に換算して
０．８μｇであった。なお、試料Ｏの比表面積は３００
ｍ2 ／ｇであり、アナタース型結晶を有しており、Ｓｃ
ｈｅｒｒｅｒの式から求めた平均粒子径は６．０ｎｍで
あった。Example 12 210 g / l containing 54 g / l iron sulfate as Fe
Was heated to a temperature of 85 ° C. and maintained for 3 hours to hydrolyze titanyl sulfate, and then nitric acid was added to adjust the pH of the solution to 1.5 to peptize.
Then, sodium hydroxide was added to the peptized solution,
The pH was adjusted to 7.0, then filtered, washed, and dried to obtain a titanium oxide photocatalyst containing the iron compound of the present invention (Sample O). This sample O was 0.025% by weight in terms of Fe based on TiO 2 weight based on titanium oxide.
Containing iron hydroxide, the surface area of the titanium oxide particles 1
The supported amount of iron hydroxide per m 2 was 0.8 μg in terms of Fe standard. The specific surface area of the sample O was 300
m 2 / g, having an anatase type crystal, Sc
The average particle diameter determined from the Herrer's formula was 6.0 nm.
【００３３】比較例４ 実施例１１において得られた試料４の酸化チタンを比較
試料Ｐとして用いた。なお、この試料４は、酸化チタン
のＴｉＯ2 重量基準に対して、Ｆｅ基準に換算して０．
０００１重量％の鉄化合物を含有していた。Comparative Example 4 The titanium oxide of Sample 4 obtained in Example 11 was used as Comparative Sample P. In addition, this sample 4 was converted to Fe standard on the basis of TiO 2 weight basis of titanium oxide, and was set to be 0.
It contained 0001% by weight of iron compound.
【００３４】実施例および比較例で得られた試料（Ｎ、
Ｏ、Ｐ）の光触媒機能を以下のようにして調べた。８０
０ｍｌの容器に試料０．０２ｇを入れた後、アセトアル
デヒドを入れて封入した。容器内のアセトアルデヒドの
濃度は約１００ｐｐｍであった。次に、ブラックライト
を１時間照射して、アセトアルデヒドを分解した。光量
は１ｍＷ／ｃｍ2 であった。試料の照射面積は１５ｃｍ
2 であった。反応中のアセトアルデヒドの濃度変化を測
定し、一次反応分解速度定数ｋを算出した。その結果を
表２に示す。この表から明らかなように、本発明の鉄化
合物を含有した酸化チタンは光触媒活性に優れているこ
とがわかった。Samples obtained in Examples and Comparative Examples (N,
The photocatalytic function of O, P) was examined as follows. 80
After placing 0.02 g of the sample in a 0 ml container, acetaldehyde was charged and sealed. The concentration of acetaldehyde in the container was about 100 ppm. Next, black light was irradiated for 1 hour to decompose acetaldehyde. The light amount was 1 mW / cm 2 . The irradiation area of the sample is 15cm
Was 2 . The change in the concentration of acetaldehyde during the reaction was measured, and the first-order reaction decomposition rate constant k was calculated. Table 2 shows the results. As is clear from this table, it was found that the titanium oxide containing the iron compound of the present invention was excellent in photocatalytic activity.
【００３５】[0035]
【表２】 [Table 2]
【００３６】実施例１３ ８０ｇ／ｌの硫酸チタニルの水溶液１リットルを８５℃
の温度に加熱し３時間保持して、硫酸チタニルを加水分
解した。このようにして得られた加水分解生成物を濾過
し、洗浄した後、水に懸濁させ、ＴｉＯ2 に換算して２
００ｇ／ｌの懸濁液とした。次いで、攪拌下、前記の懸
濁液に、フッ酸の濃度が０．１５規定になるようにフッ
酸水溶液を添加し、室温で１時間保持した後、濾過し、
濾液の電気伝導度が２００μＳ／ｃｍになるまで洗浄
し、次いで、乾燥して、本発明の酸化チタン光触媒（試
料Ｑ）を得た。なお、試料Ｑの比表面積は３１０ｍ2 ／
ｇであり、アナタース型結晶を有しており、電子顕微鏡
観察から求めた平均粒子径は３０ｎｍであった。Example 13 One liter of an aqueous solution of 80 g / l titanyl sulfate was heated to 85 ° C.
And heated for 3 hours to hydrolyze titanyl sulfate. The hydrolysis product thus obtained is filtered, washed, suspended in water and converted to TiO 2 by 2 %.
A suspension of 00 g / l was obtained. Then, under stirring, an aqueous solution of hydrofluoric acid was added to the above suspension so that the concentration of hydrofluoric acid became 0.15 N, the mixture was kept at room temperature for 1 hour, and then filtered.
The filtrate was washed until the electric conductivity reached 200 μS / cm, and then dried to obtain a titanium oxide photocatalyst of the present invention (Sample Q). The specific surface area of sample Q was 310 m 2 /
g, having an anatase crystal, and the average particle diameter determined by electron microscopic observation was 30 nm.
【００３７】実施例１４ 実施例１３において、フッ酸の濃度を０．５規定にした
こと以外、実施例１３と同様に処理して、本発明の酸化
チタン光触媒（試料Ｒ）を得た。なお、試料Ｒの比表面
積は３１０ｍ2 ／ｇであり、アナタース型結晶を有して
おり、電子顕微鏡観察から求めた平均粒子径は３０ｎｍ
であった。Example 14 A titanium oxide photocatalyst of the present invention (sample R) was obtained in the same manner as in Example 13 except that the concentration of hydrofluoric acid was changed to 0.5 N. Note that the specific surface area of the sample R was 310 m 2 / g, the sample R had an anatase crystal, and the average particle size determined from observation with an electron microscope was 30 nm.
Met.
【００３８】実施例１５ 実施例１３において、フッ酸の濃度を１．５規定にした
こと以外、実施例１３と同様に処理して、本発明の酸化
チタン光触媒（試料Ｓ）を得た。なお、試料Ｓの比表面
積は３１０ｍ2 ／ｇであり、アナタース型結晶を有して
おり、電子顕微鏡観察から求めた平均粒子径は３０ｎｍ
であった。Example 15 A titanium oxide photocatalyst of the present invention (sample S) was obtained in the same manner as in Example 13, except that the concentration of hydrofluoric acid was changed to 1.5N. Note that the specific surface area of the sample S was 310 m 2 / g, the sample S had an anatase crystal, and the average particle size determined by observation with an electron microscope was 30 nm.
Met.
【００３９】実施例１６ 実施例１４で得た試料Ｒの鉱酸処理を施した酸化チタン
１０ｇを水に懸濁させ、ＴｉＯ2 に換算して１００ｇ／
ｌの懸濁液とした。次いで、前記の懸濁液に攪拌下、塩
化鉄（ＦｅＣｌ3 ・６Ｈ2 Ｏ）１４．５ｍｇを溶解した
酸性水溶液を添加した後、アンモニア水を添加して液の
ｐＨを７．０に調整し、次いで、濾過し、濾液の電気伝
導度が２０μＳ／ｃｍになるまで洗浄し、次いで、乾燥
して、本発明の鉄化合物を担持した酸化チタン光触媒
（試料Ｔ）を得た。この試料Ｔは、酸化チタンのＴｉＯ
2 重量基準に対して、Ｆｅ基準に換算して０．０３重量
％の水酸化鉄を担持しており、酸化チタンの表面積１ｍ
2 当たりの水酸化鉄の担持量はＦｅ基準に換算して１．
０μｇであった。Example 16 10 g of the titanium oxide treated with mineral acid of the sample R obtained in Example 14 was suspended in water and converted to TiO 2 at 100 g /
1 suspension. Then, under stirring the suspension, after addition of the acidic aqueous solution prepared by dissolving ferric chloride (FeCl 3 · 6H 2 O) 14.5mg, the pH of the solution was adjusted to 7.0 by addition of aqueous ammonia Then, the mixture was filtered, washed until the filtrate had an electric conductivity of 20 μS / cm, and then dried to obtain a titanium oxide photocatalyst supporting the iron compound of the present invention (sample T). This sample T is made of titanium oxide TiO.
It supports 0.03% by weight of iron hydroxide in terms of Fe based on 2 % by weight, and has a surface area of 1 m of titanium oxide.
The supported amount of iron hydroxide per 2 is 1.
It was 0 μg.
【００４０】比較例５ ８０ｇ／ｌの硫酸チタニルの水溶液１リットルを８５℃
の温度に加熱し３時間保持して、硫酸チタニルを加水分
解した。このようにして得られた加水分解生成物を濾過
し、洗浄して、酸化チタン光触媒（試料Ｕ）を得た。な
お、試料Ｕの比表面積は３１０ｍ2 ／ｇであり、アナタ
ース型結晶を有しており、電子顕微鏡観察から求めた平
均粒子径は３０ｎｍであった。Comparative Example 5 One liter of an aqueous solution of 80 g / l titanyl sulfate was heated to 85 ° C.
And heated for 3 hours to hydrolyze titanyl sulfate. The hydrolysis product thus obtained was filtered and washed to obtain a titanium oxide photocatalyst (sample U). Sample U had a specific surface area of 310 m 2 / g, had an anatase crystal, and had an average particle diameter of 30 nm as determined from observation with an electron microscope.
【００４１】実施例および比較例で得られた試料（Ｑ〜
Ｕ）の光触媒機能を以下のようにして調べた。各試料
０．１ｇをイオン交換水に分散させ、ＴｉＯ2 に換算し
て４ｇ／ｌの懸濁液とした。これらの懸濁液２５ｍｌに
２−プロパノール２５μｌを添加した後、ブラックライ
ト（ピーク波長３６５ｎｍ）を２時間照射して、２−プ
ロパノールの光触媒反応を行った。光量は２ｍＷ／ｃｍ
2 であった。照射面積は２８ｃｍ2 であった。反応中の
２−プロパノールの濃度変化を測定し、一次反応分解速
度定数ｋを算出した。その結果を表３に示す。この表か
ら明らかなように、本発明の酸化チタン光触媒は光触媒
機能に優れていることがわかった。酸化チタンを鉱酸処
理すると、光触媒機能が著しく向上する理由については
明らかでないが、鉱酸処理によって酸化チタンに吸着す
る分解処理対象物質の量が増加しており、吸着した分解
処理対象物質と酸化チタンの光励起により生じた正孔、
電子とが速やかに反応するためと推測している。Samples obtained in Examples and Comparative Examples (Q to
The photocatalytic function of U) was examined as follows. 0.1 g of each sample was dispersed in ion-exchanged water to obtain a suspension of 4 g / l in terms of TiO 2 . After 25 μl of 2-propanol was added to 25 ml of the suspension, black light (peak wavelength: 365 nm) was irradiated for 2 hours to perform a photocatalytic reaction of 2-propanol. Light intensity is 2mW / cm
Was 2 . The irradiation area was 28 cm 2 . The change in the concentration of 2-propanol during the reaction was measured, and the first-order decomposition rate constant k was calculated. Table 3 shows the results. As is clear from this table, the titanium oxide photocatalyst of the present invention was found to be excellent in photocatalytic function. It is not clear why the photocatalytic function is significantly improved when the titanium oxide is treated with mineral acid, but the amount of the decomposition target substance adsorbed on the titanium oxide is increased by the mineral acid treatment, and the adsorbed decomposition target substance and the oxidized substance are oxidized. Holes generated by photoexcitation of titanium,
It is speculated that the reaction with the electrons occurs quickly.
【００４２】[0042]
【表３】 [Table 3]
【００４３】実施例１７ 実施例１において得られた試料１の酸化チタンを水に懸
濁させ、ＴｉＯ2 に換算して２００ｇ／ｌの懸濁液とし
た。次いで、攪拌下、前記の懸濁液に、フッ酸の濃度が
０．１５規定になるようにフッ酸水溶液を添加し、室温
で１時間保持した後、濾過し、濾液の電気伝導度が２０
０μＳ／ｃｍになるまで洗浄し、次いで、乾燥して、本
発明の酸化チタン光触媒（試料Ｖ）を得た。Example 17 The titanium oxide of Sample 1 obtained in Example 1 was suspended in water to obtain a suspension of 200 g / l in terms of TiO 2 . Next, an aqueous solution of hydrofluoric acid was added to the suspension under stirring so that the concentration of hydrofluoric acid became 0.15 N, and the mixture was maintained at room temperature for 1 hour.
The resultant was washed to 0 μS / cm and then dried to obtain a titanium oxide photocatalyst of the present invention (sample V).
【００４４】実施例１８ 実施例１７で得た試料Ｖの鉱酸処理を施した酸化チタン
１０ｇを水に懸濁させ、ＴｉＯ2 に換算して１００ｇ／
ｌの懸濁液とした。次いで、前記の懸濁液に攪拌下、塩
化鉄（ＦｅＣｌ3 ・６Ｈ2 Ｏ）８．７０ｍｇを溶解した
酸性水溶液を添加した後、アンモニア水を添加して液の
ｐＨを７．０に調整し、次いで、濾過し、洗浄し、次い
で、乾燥して、本発明の鉄化合物を含有した酸化チタン
光触媒（試料Ｗ）を得た。この試料Ｗは、酸化チタンの
ＴｉＯ2 重量基準に対して、Ｆｅ基準に換算して０．０
１８重量％の水酸化鉄を含有しており、酸化チタン粒子
の表面積１ｍ2 当たりの水酸化鉄の担持量はＦｅ基準に
換算して２．２μｇであった。Example 18 10 g of the mineral acid-treated titanium oxide of Sample V obtained in Example 17 was suspended in water and converted to TiO 2 at 100 g /
1 suspension. Then, under stirring the suspension, after addition of the acidic aqueous solution prepared by dissolving ferric chloride (FeCl 3 · 6H 2 O) 8.70mg, the pH of the solution was adjusted to 7.0 by addition of aqueous ammonia Then, the resultant was filtered, washed, and dried to obtain a titanium oxide photocatalyst (sample W) containing the iron compound of the present invention. This sample W was 0.0% in terms of Fe based on the TiO 2 weight basis of titanium oxide.
It contained 18% by weight of iron hydroxide, and the amount of iron hydroxide supported per 1 m 2 of surface area of the titanium oxide particles was 2.2 μg in terms of Fe standard.
【００４５】実施例および比較例で得られた試料（Ｃ、
Ｅ、Ｖ、Ｗ）の光触媒機能を以下のようにして調べた。
各試料０．１ｇをイオン交換水に分散させ、ＴｉＯ2 に
換算して４ｇ／ｌの懸濁液とした。これらの懸濁液２５
ｍｌに２−プロパノール２５μｌを添加した後、ブラッ
クライトを２時間照射して、２−プロパノールの光触媒
反応を行った。光量は２ｍＷ／ｃｍ2 であった。照射面
積は２８ｃｍ2 であった。反応中の２−プロパノールの
濃度変化を測定し、一次反応分解速度定数ｋを算出し
た。その結果を表４に示す。この表から明らかなよう
に、本発明の酸化チタン光触媒は光触媒活性に優れてい
ることがわかった。特に、鉱酸処理した酸化チタン粒子
の表面に鉄化合物を担持した酸化チタン光触媒は、鉱酸
処理と鉄化合物の担持処理との相乗効果により、優れた
光触媒活性を有することがわかった。The samples (C, C) obtained in Examples and Comparative Examples
E, V, W) were examined for photocatalytic function as follows.
0.1 g of each sample was dispersed in ion-exchanged water to obtain a suspension of 4 g / l in terms of TiO 2 . These suspensions 25
After adding 25 μl of 2-propanol to the resulting mixture, the mixture was irradiated with black light for 2 hours to perform a photocatalytic reaction of 2-propanol. The light amount was 2 mW / cm 2 . The irradiation area was 28 cm 2 . The change in the concentration of 2-propanol during the reaction was measured, and the first-order decomposition rate constant k was calculated. Table 4 shows the results. As is clear from this table, it was found that the titanium oxide photocatalyst of the present invention was excellent in photocatalytic activity. In particular, it has been found that the titanium oxide photocatalyst in which an iron compound is supported on the surface of the titanium oxide particles subjected to the mineral acid treatment has excellent photocatalytic activity due to the synergistic effect of the mineral acid treatment and the treatment for supporting the iron compound.
【００４６】[0046]
【表４】 [Table 4]
【００４７】[0047]
【発明の効果】本発明の酸化チタン光触媒は、酸化チタ
ン粒子の内部および／またはその表面に鉄化合物を含有
してなるものであって、鉄化合物を含有させることによ
り酸化チタンの光触媒機能を向上させることができる。
また、本発明の酸化チタン光触媒は、酸化チタンを鉱酸
処理してなるものであって、酸化チタンの光触媒機能を
向上させることができる。更に、本発明の酸化チタン光
触媒は、鉱酸処理を施した酸化チタン粒子の内部および
／またはその表面に鉄化合物を含有してなるものであっ
て、酸化チタンの光触媒機能を一層向上させることがで
きる。それらの光触媒機能を利用して人体や生活環境に
悪影響を及ぼす物質やその可能性がある物質を迅速、か
つ、効率よく除去することができるので、工業用途ばか
りでなく一般家庭用の脱臭体、殺菌体などとして極めて
有用なものである。また、本発明の酸化チタン光触媒
は、安全性が高く、さらに、廃棄しても環境を汚さない
ため、種々の用途に用いることができる。The titanium oxide photocatalyst of the present invention contains an iron compound inside and / or on the surface of titanium oxide particles, and the photocatalytic function of titanium oxide is improved by containing the iron compound. Can be done.
The titanium oxide photocatalyst of the present invention is obtained by treating titanium oxide with a mineral acid, and can improve the photocatalytic function of titanium oxide. Further, the titanium oxide photocatalyst of the present invention contains an iron compound inside and / or on the surface of the titanium oxide particles subjected to the mineral acid treatment, and can further improve the photocatalytic function of the titanium oxide. it can. By using these photocatalytic functions, substances that adversely affect the human body and living environment and substances that may be affected can be quickly and efficiently removed, so that not only industrial uses but also general household deodorants, It is extremely useful as a sterile body. Further, the titanium oxide photocatalyst of the present invention has high safety and does not pollute the environment even when disposed, so that it can be used for various applications.
【００４８】次に、本発明は前記の光触媒用酸化チタン
の製造方法であって、優れた光触媒機能を有する酸化チ
タンを簡便、かつ、効率よく製造することができるな
ど、工業的に有用な方法である。Next, the present invention relates to a method for producing the above-mentioned titanium oxide for photocatalyst, which is an industrially useful method such that titanium oxide having an excellent photocatalytic function can be produced simply and efficiently. It is.
───────────────────────────────────────────────────── フロントページの続き (56)参考文献 特開 平６−279026（ＪＰ，Ａ) (58)調査した分野(Int.Cl.6，ＤＢ名) B01J 23/745 B01D 53/86 B01J 35/02 ──────────────────────────────────────────────────続 き Continuation of the front page (56) References JP-A-6-279026 (JP, A) (58) Fields investigated (Int. Cl. 6 , DB name) B01J 23/745 B01D 53/86 B01J 35 / 02
Claims (20)
は中和して得られる酸化チタン粒子の内部および／また
はその表面に鉄化合物を含有してなることを特徴とする
光触媒用酸化チタン。1. A method of hydrolyzing a titanium compound in an aqueous solution.
Is a titanium oxide for a photocatalyst, characterized by containing an iron compound inside and / or on the surface of titanium oxide particles obtained by neutralization .
タン粒子であることを特徴とする請求項１に記載の光触
媒用酸化チタン。2. The titanium oxide for photocatalyst according to claim 1, wherein the titanium oxide particles are titanium oxide particles treated with a mineral acid.
項２に記載の光触媒用酸化チタン。3. The titanium oxide for photocatalyst according to claim 2, wherein the mineral acid is hydrofluoric acid.
化合物であることを特徴とする請求項１に記載の光触媒
用酸化チタン。4. The titanium oxide for a photocatalyst according to claim 1, wherein the iron compound is a trivalent and / or divalent iron compound.
ｎｍであることを特徴とする請求項１に記載の光触媒用
酸化チタン。5. The titanium oxide particles have an average particle size of 1 to 500.
2. The titanium oxide for photocatalyst according to claim 1, wherein:
て、鉄化合物をＦｅ基準に換算して０．０００５〜１０
重量％含有してなることを特徴とする請求項１に記載の
光触媒用酸化チタン。6. The iron compound is converted to Fe based on 0.002 to 10 based on the weight of TiO 2 of the titanium oxide particles.
The titanium oxide for a photocatalyst according to claim 1, which is contained by weight%.
て、鉄化合物をＦｅ基準に換算して０．００１〜５重量
％含有してなることを特徴とする請求項１に記載の光触
媒用酸化チタン。7. The photocatalyst according to claim 1, wherein the titanium oxide particles contain 0.001 to 5% by weight of an iron compound in terms of Fe based on 2 % by weight of TiO. Titanium oxide.
ｅ基準に換算して０．０５〜５０００μｇの量の鉄化合
物を酸化チタン粒子の表面に担持してなることを特徴と
する請求項１に記載の光触媒用酸化チタン。8. surface area 1 m 2 per titanium oxide particles, F
2. The titanium oxide for a photocatalyst according to claim 1, wherein an iron compound in an amount of 0.05 to 5000 [mu] g in terms of e is supported on the surface of the titanium oxide particles.
ｅ基準に換算して０．１〜３０００μｇの量の鉄化合物
を酸化チタン粒子の表面に担持してなることを特徴とす
る請求項１に記載の光触媒用酸化チタン。9. The titanium oxide particles have a surface area of 1 m 2 ,
2. The titanium oxide for photocatalyst according to claim 1, wherein an amount of 0.1 to 3000 [mu] g of an iron compound in terms of e standard is supported on the surface of the titanium oxide particles.
あることを特徴とする請求項１に記載の光触媒用酸化チ
タン。10. The titanium oxide for a photocatalyst according to claim 1, wherein the titanium oxide is an anatase type titanium oxide.
を特徴とする光触媒用酸化チタン。11. A titanium oxide for a photocatalyst, comprising titanium oxide treated with a mineral acid.
求項１１に記載の光触媒用酸化チタン。12. The titanium oxide for photocatalyst according to claim 11, wherein the mineral acid is hydrofluoric acid.
あることを特徴とする請求項１１に記載の光触媒用酸化
チタン。13. The titanium oxide for a photocatalyst according to claim 11, wherein the titanium oxide is an anatase type titanium oxide.
ｎｍであることを特徴とする請求項１１に記載の光触媒
用酸化チタン。14. The titanium oxide has an average particle size of 1 to 1000.
The titanium oxide for a photocatalyst according to claim 11, wherein
液中で加水分解あるいは中和することを特徴とする請求
項１に記載の光触媒用酸化チタンの製造方法。15. A method for dissolving a titanium compound in water in the presence of an iron compound.
The method for producing titanium oxide for a photocatalyst according to claim 1 , wherein hydrolysis or neutralization is performed in a liquid .
いは中和して酸化チタンを得、次いで、該酸化チタンを
鉄化合物の溶液に浸漬することを特徴とする請求項１に
記載の光触媒用酸化チタンの製造方法。16. The oxidation according to claim 1, wherein the titanium compound is hydrolyzed or neutralized in an aqueous solution to obtain titanium oxide, and then the titanium oxide is immersed in a solution of an iron compound. Manufacturing method of titanium.
液に浸漬することを特徴とする請求項１に記載の光触媒
用酸化チタンの製造方法。17. The method for producing titanium oxide for a photocatalyst according to claim 1, wherein the titanium oxide treated with a mineral acid is immersed in a solution of an iron compound.
て酸化チタンを得、次いで、該酸化チタンを鉱酸処理す
ることを特徴とする請求項１７に記載の光触媒用酸化チ
タンの製造方法。18. The method for producing a titanium oxide for a photocatalyst according to claim 17, wherein the titanium compound is hydrolyzed or neutralized to obtain titanium oxide, and then the titanium oxide is treated with a mineral acid.
て酸化チタンを得、次いで、該酸化チタンを鉱酸処理す
ることを特徴とする請求項１１に記載の光触媒用酸化チ
タンの製造方法。19. The method for producing titanium oxide for a photocatalyst according to claim 11, wherein the titanium compound is hydrolyzed or neutralized to obtain titanium oxide, and then the titanium oxide is treated with a mineral acid.
の水溶液の沸点温度以下で行うことを特徴とする請求項
１５、１６、１８または１９のいずれか１項に記載の光
触媒用酸化チタンの製造方法。20. The method for producing titanium oxide for a photocatalyst according to claim 15, wherein the hydrolysis of the titanium compound is carried out at a temperature not higher than the boiling point of the aqueous solution of the titanium compound. .
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| CN116113494A (en) | 2020-09-15 | 2023-05-12 | 信越化学工业株式会社 | Titanium oxide particles, dispersion thereof, photocatalyst film, member having photocatalyst film on surface, and method for producing titanium oxide particle dispersion |
| TW202311168A (en) | 2021-04-21 | 2023-03-16 | 日商信越化學工業股份有限公司 | Titanium oxide particle-metal particle composition and manufacturing method therefor |
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-
1995
- 1995-02-07 JP JP7043582A patent/JP2909403B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPH07303835A (en) | 1995-11-21 |
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