JP2012110831A - Photocatalyst for decomposing volatile aromatic compound, and product having photocatalytic function - Google Patents
Photocatalyst for decomposing volatile aromatic compound, and product having photocatalytic function Download PDFInfo
- Publication number
- JP2012110831A JP2012110831A JP2010261667A JP2010261667A JP2012110831A JP 2012110831 A JP2012110831 A JP 2012110831A JP 2010261667 A JP2010261667 A JP 2010261667A JP 2010261667 A JP2010261667 A JP 2010261667A JP 2012110831 A JP2012110831 A JP 2012110831A
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- JP
- Japan
- Prior art keywords
- oxide particles
- photocatalyst
- tungsten oxide
- titanium
- volatile aromatic
- 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.)
- Pending
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- 239000011941 photocatalyst Substances 0.000 title claims abstract description 90
- 230000001699 photocatalysis Effects 0.000 title claims abstract description 46
- 150000001491 aromatic compounds Chemical class 0.000 title claims abstract description 43
- 239000002245 particle Substances 0.000 claims abstract description 152
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 claims abstract description 101
- 229910001930 tungsten oxide Inorganic materials 0.000 claims abstract description 101
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 75
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims abstract description 75
- 239000010936 titanium Substances 0.000 claims abstract description 23
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 16
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000011248 coating agent Substances 0.000 claims abstract description 12
- 238000000576 coating method Methods 0.000 claims abstract description 12
- 239000006185 dispersion Substances 0.000 claims description 34
- 239000000126 substance Substances 0.000 claims description 28
- 239000002243 precursor Substances 0.000 claims description 23
- 238000000354 decomposition reaction Methods 0.000 claims description 20
- 239000010949 copper Substances 0.000 claims description 12
- 239000002612 dispersion medium Substances 0.000 claims description 11
- 239000007788 liquid Substances 0.000 claims description 10
- 229910052751 metal Inorganic materials 0.000 claims description 9
- 239000002184 metal Substances 0.000 claims description 9
- 229910052697 platinum Inorganic materials 0.000 claims description 8
- 229910052737 gold Inorganic materials 0.000 claims description 6
- 229910052763 palladium Inorganic materials 0.000 claims description 6
- 239000000758 substrate Substances 0.000 claims description 6
- 229910052802 copper Inorganic materials 0.000 claims description 5
- 229910052741 iridium Inorganic materials 0.000 claims description 4
- 229910052742 iron Inorganic materials 0.000 claims description 4
- 229910052758 niobium Inorganic materials 0.000 claims description 4
- 229910052703 rhodium Inorganic materials 0.000 claims description 4
- 229910052707 ruthenium Inorganic materials 0.000 claims description 4
- 229910052709 silver Inorganic materials 0.000 claims description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 83
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 28
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 21
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 21
- 238000000034 method Methods 0.000 description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 19
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- 239000000463 material Substances 0.000 description 18
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- 239000007789 gas Substances 0.000 description 15
- 239000001569 carbon dioxide Substances 0.000 description 14
- 229910002092 carbon dioxide Inorganic materials 0.000 description 14
- 239000003960 organic solvent Substances 0.000 description 11
- ZNOKGRXACCSDPY-UHFFFAOYSA-N tungsten trioxide Chemical compound O=[W](=O)=O ZNOKGRXACCSDPY-UHFFFAOYSA-N 0.000 description 10
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- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 8
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- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
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- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 2
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
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- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 239000003125 aqueous solvent Substances 0.000 description 2
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Chemical compound [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 description 2
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- 229920001296 polysiloxane Polymers 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- IATRAKWUXMZMIY-UHFFFAOYSA-N strontium oxide Chemical compound [O-2].[Sr+2] IATRAKWUXMZMIY-UHFFFAOYSA-N 0.000 description 2
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- FWBOFUGDKHMVPI-UHFFFAOYSA-K dicopper;2-oxidopropane-1,2,3-tricarboxylate Chemical compound [Cu+2].[Cu+2].[O-]C(=O)CC([O-])(C([O-])=O)CC([O-])=O FWBOFUGDKHMVPI-UHFFFAOYSA-K 0.000 description 1
- SKQUUKNCBWILCD-UHFFFAOYSA-J dicopper;chloride;trihydroxide Chemical compound [OH-].[OH-].[OH-].[Cl-].[Cu+2].[Cu+2] SKQUUKNCBWILCD-UHFFFAOYSA-J 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- XGZNHFPFJRZBBT-UHFFFAOYSA-N ethanol;titanium Chemical compound [Ti].CCO.CCO.CCO.CCO XGZNHFPFJRZBBT-UHFFFAOYSA-N 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
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- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 239000003517 fume Substances 0.000 description 1
- 239000007792 gaseous phase Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- FDWREHZXQUYJFJ-UHFFFAOYSA-M gold monochloride Chemical compound [Cl-].[Au+] FDWREHZXQUYJFJ-UHFFFAOYSA-M 0.000 description 1
- 229910001922 gold oxide Inorganic materials 0.000 description 1
- KPQDSKZQRXHKHY-UHFFFAOYSA-N gold potassium Chemical compound [K].[Au] KPQDSKZQRXHKHY-UHFFFAOYSA-N 0.000 description 1
- 229910021505 gold(III) hydroxide Inorganic materials 0.000 description 1
- WDZVNNYQBQRJRX-UHFFFAOYSA-K gold(iii) hydroxide Chemical compound O[Au](O)O WDZVNNYQBQRJRX-UHFFFAOYSA-K 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910002094 inorganic tetrachloropalladate Inorganic materials 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- YWXYYJSYQOXTPL-SLPGGIOYSA-N isosorbide mononitrate Chemical compound [O-][N+](=O)O[C@@H]1CO[C@@H]2[C@@H](O)CO[C@@H]21 YWXYYJSYQOXTPL-SLPGGIOYSA-N 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 229910052622 kaolinite Inorganic materials 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 150000004692 metal hydroxides Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- ZEIWWVGGEOHESL-UHFFFAOYSA-N methanol;titanium Chemical compound [Ti].OC.OC.OC.OC ZEIWWVGGEOHESL-UHFFFAOYSA-N 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- HBEQXAKJSGXAIQ-UHFFFAOYSA-N oxopalladium Chemical compound [Pd]=O HBEQXAKJSGXAIQ-UHFFFAOYSA-N 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- NXJCBFBQEVOTOW-UHFFFAOYSA-L palladium(2+);dihydroxide Chemical compound O[Pd]O NXJCBFBQEVOTOW-UHFFFAOYSA-L 0.000 description 1
- RFLFDJSIZCCYIP-UHFFFAOYSA-L palladium(2+);sulfate Chemical compound [Pd+2].[O-]S([O-])(=O)=O RFLFDJSIZCCYIP-UHFFFAOYSA-L 0.000 description 1
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 1
- YJVFFLUZDVXJQI-UHFFFAOYSA-L palladium(ii) acetate Chemical compound [Pd+2].CC([O-])=O.CC([O-])=O YJVFFLUZDVXJQI-UHFFFAOYSA-L 0.000 description 1
- INIOZDBICVTGEO-UHFFFAOYSA-L palladium(ii) bromide Chemical compound Br[Pd]Br INIOZDBICVTGEO-UHFFFAOYSA-L 0.000 description 1
- GPNDARIEYHPYAY-UHFFFAOYSA-N palladium(ii) nitrate Chemical compound [Pd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O GPNDARIEYHPYAY-UHFFFAOYSA-N 0.000 description 1
- 239000000123 paper Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 230000001443 photoexcitation Effects 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 238000005240 physical vapour deposition Methods 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- CLSUSRZJUQMOHH-UHFFFAOYSA-L platinum dichloride Chemical compound Cl[Pt]Cl CLSUSRZJUQMOHH-UHFFFAOYSA-L 0.000 description 1
- KABWJWZACJCALW-UHFFFAOYSA-J platinum tetrachloroplatinum Chemical compound Cl[Pt](Cl)(Cl)Cl.[Pt] KABWJWZACJCALW-UHFFFAOYSA-J 0.000 description 1
- KGRJUMGAEQQVFK-UHFFFAOYSA-L platinum(2+);dibromide Chemical compound Br[Pt]Br KGRJUMGAEQQVFK-UHFFFAOYSA-L 0.000 description 1
- ZXDJCKVQKCNWEI-UHFFFAOYSA-L platinum(2+);diiodide Chemical compound [I-].[I-].[Pt+2] ZXDJCKVQKCNWEI-UHFFFAOYSA-L 0.000 description 1
- AAIMUHANAAXZIF-UHFFFAOYSA-L platinum(2+);sulfite Chemical compound [Pt+2].[O-]S([O-])=O AAIMUHANAAXZIF-UHFFFAOYSA-L 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 235000019353 potassium silicate Nutrition 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000000790 scattering method Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 208000008842 sick building syndrome Diseases 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 150000003377 silicon compounds Chemical class 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000012798 spherical particle Substances 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- UUCCCPNEFXQJEL-UHFFFAOYSA-L strontium dihydroxide Chemical compound [OH-].[OH-].[Sr+2] UUCCCPNEFXQJEL-UHFFFAOYSA-L 0.000 description 1
- 229910001866 strontium hydroxide Inorganic materials 0.000 description 1
- 239000001384 succinic acid Substances 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 238000009210 therapy by ultrasound Methods 0.000 description 1
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 1
- 150000003609 titanium compounds Chemical class 0.000 description 1
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 description 1
- GCZKMPJFYKFENV-UHFFFAOYSA-K triiodogold Chemical compound I[Au](I)I GCZKMPJFYKFENV-UHFFFAOYSA-K 0.000 description 1
- PBYZMCDFOULPGH-UHFFFAOYSA-N tungstate Chemical compound [O-][W]([O-])(=O)=O PBYZMCDFOULPGH-UHFFFAOYSA-N 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 238000001771 vacuum deposition Methods 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
Abstract
Description
本発明は、気相中に含まれる揮発性芳香族化合物を速やかに分解し得る揮発性芳香族化合物分解用光触媒体と、該光触媒体を用いた光触媒機能製品とに関する。 The present invention relates to a photocatalyst for decomposing volatile aromatic compounds capable of rapidly decomposing volatile aromatic compounds contained in a gas phase, and a photocatalytic functional product using the photocatalyst.
半導体にバンドギャップ以上のエネルギーを持つ光を照射すると、価電子帯の電子が伝導帯に励起されるとともに、価電子帯に正孔が生成する。かかる励起電子および正孔は、それぞれ強い還元力と酸化力とを有することから、半導体に接触した分子種に酸化還元作用を及ぼす。この酸化還元作用は光触媒作用と呼ばれており、かかる光触媒作用を示し得る半導体は、光触媒体と呼ばれている。 When a semiconductor is irradiated with light having energy greater than or equal to the band gap, electrons in the valence band are excited to the conduction band and holes are generated in the valence band. Such excited electrons and holes have a strong reducing power and oxidizing power, respectively, and therefore exert a redox action on molecular species in contact with the semiconductor. This redox action is called a photocatalytic action, and a semiconductor that can exhibit such a photocatalytic action is called a photocatalyst.
このような光触媒体としては、従来、酸化タングステン粒子や酸化チタン粒子が知られており、これらの光触媒作用は、気相中の有害物質である揮発性有機化合物を二酸化炭素などに分解し除去するのに利用されている。例えば、これまでに、酸化タングステン粒子および酸化チタン粒子からなる光触媒体を分散させたコーティング液が提案されており（特許文献１参照）、このコーティング液を基材の表面に塗布することにより形成される光触媒体層に、気相中の揮発性有機化合物を光照射下で接触させることによって、該揮発性有機化合物を分解させることができる。 Conventionally known as such photocatalysts are tungsten oxide particles and titanium oxide particles, and these photocatalytic actions decompose and remove volatile organic compounds, which are harmful substances in the gas phase, into carbon dioxide and the like. It is used for. For example, a coating liquid in which a photocatalyst composed of tungsten oxide particles and titanium oxide particles is dispersed has been proposed so far (see Patent Document 1), and is formed by applying this coating liquid to the surface of a substrate. The volatile organic compound can be decomposed by contacting the photocatalyst layer with a volatile organic compound in the gas phase under light irradiation.
しかしながら、光触媒作用により分解しようとする化合物がトルエン、キシレン等の揮発性芳香族化合物である場合、従来の光触媒体を用いると、芳香族化合物が分解される過程で光触媒体の表面に芳香族化合物由来の分解生成物などが吸着して活性点が覆われてしまい、光触媒活性が経時的に低下して、気相中の芳香族化合物を完全に二酸化炭素に分解するまでに長時間を要することがある。
一方、上記揮発性芳香族化合物は、建材、内装材、電気製品などに使用される塗料や接着剤の溶剤などに広く使用されているが、揮発性芳香族化合物の人体に対する影響が問題視されており、シックハウス症候群の原因物質の１つであるといわれている。
However, when the compound to be decomposed by the photocatalytic action is a volatile aromatic compound such as toluene or xylene, using the conventional photocatalyst, the aromatic compound is formed on the surface of the photocatalyst during the process of decomposing the aromatic compound. It takes a long time to decompose the aromatic compounds in the gas phase completely into carbon dioxide, as the decomposition products derived from them are adsorbed and the active sites are covered, and the photocatalytic activity decreases with time. There is.
On the other hand, the volatile aromatic compounds are widely used in paints and adhesive solvents used for building materials, interior materials, electrical products, etc., but the effect of volatile aromatic compounds on the human body is regarded as a problem. It is said to be one of the causative substances of sick house syndrome.
すなわち、本発明の課題は、気相中の揮発性芳香族化合物を速やかに分解し得る揮発性芳香族化合物分解用光触媒体と、該光触媒体を用いた光触媒機能製品とを提供することにある。 That is, the subject of this invention is providing the photocatalyst body for volatile aromatic compound decomposition | disassembly which can decompose | disassemble the volatile aromatic compound in a gaseous phase rapidly, and a photocatalyst functional product using this photocatalyst body. .
本発明者等は、前記課題を解決すべく鋭意検討を行った。その結果、酸化タングステン粒子を主成分として含有し、前記酸化タングステン粒子の表面を酸化チタン粒子で被覆されており、前記酸化チタン粒子の含有量が、酸化タングステン粒子１００質量部に対してチタン換算で３〜４５質量部である光触媒体が、顕著な効果を発揮することを見出した。 The present inventors have intensively studied to solve the above problems. As a result, it contains tungsten oxide particles as a main component, the surface of the tungsten oxide particles is coated with titanium oxide particles, and the content of the titanium oxide particles in terms of titanium with respect to 100 parts by mass of the tungsten oxide particles. It has been found that a photocatalyst having 3 to 45 parts by mass exhibits a remarkable effect.
すなわち、本発明は、以下の構成からなる。
（１）気相中の揮発性芳香族化合物を分解するための光触媒体であって、酸化タングステン粒子を主成分として含有し、前記酸化タングステン粒子の表面を酸化チタン粒子で被覆されており、前記酸化チタン粒子の被覆量が、前記酸化タングステン粒子１００質量部に対して、チタン換算で３〜４５質量部であることを特徴とする揮発性芳香族化合物分解用光触媒体。
（２）前記酸化タングステン粒子および前記酸化チタン粒子の少なくとも一方に電子吸引性物質およびその前駆体の少なくとも一方が担持されていることを特徴とする前記（１）に記載の揮発性芳香族化合物分解用光触媒体。
（３）前記電子吸引性物質またはその前駆体が、Ｃｕ、Ｐｔ、Ａｕ、Ｐｄ、Ａｇ、Ｆｅ、Ｎｂ、Ｒｕ、Ｉｒ、ＲｈおよびＣｏから選ばれる少なくとも１種の金属原子を含有してなるものである前記（２）に記載の揮発性芳香族化合物分解用光触媒体。
（４）前記（１）〜（３）のいずれかに記載の光触媒体と分散媒とを少なくとも含む揮発性芳香族化合物分解用光触媒体分散液。
（５）基材の表面に前記（１）〜（３）のいずれかに記載の光触媒体で形成された光触媒体層を備えていることを特徴とする光触媒機能製品。
That is, this invention consists of the following structures.
(1) A photocatalyst for decomposing a volatile aromatic compound in a gas phase, containing tungsten oxide particles as a main component, the surface of the tungsten oxide particles being coated with titanium oxide particles, The photocatalyst for volatile aromatic compound decomposition, wherein the coating amount of titanium oxide particles is 3 to 45 parts by mass in terms of titanium with respect to 100 parts by mass of the tungsten oxide particles.
(2) The volatile aromatic compound decomposition according to (1), wherein at least one of an electron-withdrawing substance and a precursor thereof is supported on at least one of the tungsten oxide particles and the titanium oxide particles. Photocatalyst for use.
(3) The electron withdrawing substance or its precursor contains at least one metal atom selected from Cu, Pt, Au, Pd, Ag, Fe, Nb, Ru, Ir, Rh and Co. The photocatalyst for volatile aromatic compound decomposition according to (2) above.
(4) A photocatalyst dispersion liquid for decomposing volatile aromatic compounds, comprising at least the photocatalyst according to any one of (1) to (3) and a dispersion medium.
(5) A photocatalytic functional product comprising a photocatalyst layer formed of the photocatalyst according to any one of (1) to (3) on a surface of a base material.
本発明によれば、気相中の揮発性芳香族化合物を光の照射下で速やかに分解することができる。 According to the present invention, a volatile aromatic compound in a gas phase can be rapidly decomposed under light irradiation.
本発明の揮発性芳香族化合物分解用光触媒体（以下、単に「本発明の光触媒体」と称する）は、酸化タングステン粒子の表面が酸化チタン粒子で被覆された光触媒体であり、酸化チタン粒子の被覆量が所定量であるものである。 The photocatalyst for decomposing volatile aromatic compounds of the present invention (hereinafter simply referred to as “photocatalyst of the present invention”) is a photocatalyst in which the surfaces of tungsten oxide particles are coated with titanium oxide particles. The covering amount is a predetermined amount.
本発明における酸化タングステン粒子は、光触媒作用を示す粒子状の酸化タングステンであれば、特に制限はされないが、例えば、三酸化タングステン〔ＷＯ3〕粒子等が挙げられる。なお、酸化タングステン粒子は、１種のみであってもよいし、２種以上であってもよい。 The tungsten oxide particles in the present invention are not particularly limited as long as they are particulate tungsten oxide exhibiting a photocatalytic action, and examples thereof include tungsten trioxide [WO 3 ] particles. The tungsten oxide particles may be only one type or two or more types.
三酸化タングステン粒子は、例えば、（１−ｉ）タングステン酸塩の水溶液に酸を加えることにより、沈殿物としてタングステン酸を得、得られたタングステン酸を焼成する方法、（１−ｉｉ）メタタングステン酸アンモニウムやパラタングステン酸アンモニウムを加熱することにより熱分解する方法、（１−ｉｉｉ）金属状のタングステン粒子を焼成する方法などによって得ることができる。
本発明における酸化タングステン粒子のＢＥＴ比表面積は、特に制限されないが、光触媒作用の観点から、通常５〜１００ｍ2／ｇ、好ましくは８〜５０ｍ2／ｇであるのがよい。
The tungsten trioxide particles are obtained by, for example, (1-i) a method of adding tungstic acid as a precipitate by adding an acid to an aqueous solution of tungstate and firing the obtained tungstic acid, (1-ii) metatungsten It can be obtained by a method of thermally decomposing by heating ammonium acid ammonium or ammonium paratungstate, or a method of firing (1-iii) metallic tungsten particles.
BET specific surface area of the tungsten oxide particles in the present invention is not particularly limited, from the viewpoint of photocatalytic activity, typically 5 to 100 m 2 / g, it's good preferably 8~50m 2 / g.
本発明の光触媒体は、酸化タングステン粒子の表面が、酸化チタン粒子で被覆されている。これにより、光触媒体は、例えば、表面に酸化チタン粒子を被覆していない酸化タングステン粒子より、可視光が照射された後、高い光触媒作用を持続する。
ここで、被覆とは、酸化タングステン粒子の表面の少なくとも一部に酸化チタン粒子が存在し、かつ該表面に酸化チタン粒子が存在していない部分が存在することを意味する。「酸化タングステン粒子の表面に酸化チタン粒子が存在していない部分が存在する」とは、例えば、酸化タングステン粒子の表面全面に酸化チタン粒子が被覆されておらず、酸化タングステン粒子が受光表面を有することである。これは、酸化タングステン粒子の表面全面に酸化チタン粒子が被覆されていると、可視光照射下において、本発明の光触媒体より極端に低い光触媒作用を示すためである。
In the photocatalyst of the present invention, the surface of tungsten oxide particles is coated with titanium oxide particles. Thereby, a photocatalyst body maintains a high photocatalytic action, for example, after being irradiated with visible light from tungsten oxide particles whose surfaces are not coated with titanium oxide particles.
Here, the term “coating” means that titanium oxide particles are present on at least a part of the surface of the tungsten oxide particles, and there are portions where no titanium oxide particles are present on the surface. “There is a portion where the titanium oxide particles do not exist on the surface of the tungsten oxide particles” means, for example, that the entire surface of the tungsten oxide particles is not coated with the titanium oxide particles, and the tungsten oxide particles have a light receiving surface. That is. This is because when the surface of the tungsten oxide particles is coated with titanium oxide particles, the photocatalytic action is extremely lower than that of the photocatalyst of the present invention under visible light irradiation.
酸化チタン粒子におけるチタンの原料としては、例えば、テトラエトキシチタン、テトライソプロポキシチタン、テトラｎ−プロポキシチタン、テトラブトキシチタン、テトラメトキシチタンなどのチタンのアルコキシドや、チタンジイソプロポキシビス（アセチルアセトネート）、チタンテトラアセチルアセトネート、チタンジオクチロキシビス（オクチレングリコレート）、チタンジイソプロポキシビス（エチルアセトアセテート）、チタンジイソプロポキシビス（トリエタノールアミネート）、チタンラクテートアンモニウム、チタンラクテートや、特開2006-182616号公報に記載されているチタン化合物が挙げられる。 Examples of the titanium raw material in the titanium oxide particles include titanium alkoxides such as tetraethoxy titanium, tetraisopropoxy titanium, tetra n-propoxy titanium, tetrabutoxy titanium, tetramethoxy titanium, and titanium diisopropoxy bis (acetylacetonate). ), Titanium tetraacetylacetonate, titanium dioctyloxybis (octylene glycolate), titanium diisopropoxybis (ethyl acetoacetate), titanium diisopropoxybis (triethanolaminate), titanium lactate ammonium, titanium lactate and And titanium compounds described in JP-A-2006-182616.
酸化タングステン粒子の表面に酸化チタン粒子を被覆させる方法としては、例えば、チタンラクテートなどの上述したチタンの原料を含む溶液中に酸化タングステン粒子を分散させ、これを乾燥して溶媒を除去した後、得られた粉末を空気中で焼成する方法などが挙げられる。 As a method of coating the surface of the tungsten oxide particles with the titanium oxide particles, for example, the tungsten oxide particles are dispersed in a solution containing the above-described titanium raw material such as titanium lactate, and after drying and removing the solvent, The method of baking the obtained powder in the air etc. are mentioned.
空気中での焼成は、２８０〜５８０℃の範囲で行うのが好ましい。焼成温度が２８０℃よりも低い場合、酸化チタン粒子中にチタンの原料由来の不純物（例えば炭素）が残留し、得られる光触媒体は十分な光触媒活性を発現しないおそれがある。一方、焼成温度が５８０℃を越えると、酸化チタン粒子及び酸化タングステン粒子の焼結が進み、表面積が低下する為、得られる光触媒体は十分な光触媒活性を発現しないおそれがある。 Firing in air is preferably performed in the range of 280 to 580 ° C. When the calcination temperature is lower than 280 ° C., impurities (for example, carbon) derived from the titanium raw material remain in the titanium oxide particles, and the resulting photocatalyst may not exhibit sufficient photocatalytic activity. On the other hand, when the firing temperature exceeds 580 ° C., the sintering of the titanium oxide particles and the tungsten oxide particles proceeds and the surface area decreases, so that the resulting photocatalyst may not exhibit sufficient photocatalytic activity.
酸化チタン粒子の被覆量（含有量）は、酸化タングステン粒子１００質量部に対して、チタン（Ｔｉ）換算で３〜４５質量部の範囲である。酸化チタン粒子の被覆量が３質量部未満の場合、得られる光触媒体は揮発性芳香族化合物に対して十分な光触媒活性を発現せず、一方、被覆量が４５質量部を越えると、酸化タングステンの表面を被覆する酸化チタン粒子の量が多くなり、酸化タングステンが吸収する可視光線の量が少なくなる為、得られる光触媒体は特に可視光線照射下で十分な光触媒活性を発現しないおそれがある。
なお、酸化チタン粒子の含有量は上記範囲内であるため、本発明の光触媒体において酸化タングステン粒子が主成分となる。
The coating amount (content) of the titanium oxide particles is in the range of 3 to 45 parts by mass in terms of titanium (Ti) with respect to 100 parts by mass of the tungsten oxide particles. When the coating amount of titanium oxide particles is less than 3 parts by mass, the resulting photocatalyst does not exhibit sufficient photocatalytic activity for volatile aromatic compounds, while when the coating amount exceeds 45 parts by mass, tungsten oxide Since the amount of titanium oxide particles covering the surface of the material increases and the amount of visible light absorbed by tungsten oxide decreases, the resulting photocatalyst may not exhibit sufficient photocatalytic activity particularly under visible light irradiation.
In addition, since the content of the titanium oxide particles is within the above range, the tungsten oxide particles are the main component in the photocatalyst of the present invention.
本発明の光触媒体は、その表面に、すなわち酸化タングステン粒子および酸化チタン粒子の表面の少なくとも一方に、電子吸引性物質およびその前駆体の少なくとも一方が担持されるのが好ましい。これにより、光照射によって伝導帯に励起された電子と価電子帯に生成した正孔との再結合が抑制され、酸化チタン被覆酸化タングステン粒子の光触媒活性をより高めることができる。
なお、電子吸引性物質とは、光触媒体（すなわち、酸化チタン粒子および酸化タングステン粒子）の表面に担持されて電子吸引性を発揮しうる化合物であり、電子吸引性物質の前駆体とは、光触媒体の表面で電子吸引性物質に遷移しうる化合物（例えば、光照射により電子吸引性物質に還元されうる化合物）である。
In the photocatalyst of the present invention, it is preferable that at least one of the electron withdrawing substance and the precursor thereof is supported on the surface thereof, that is, at least one of the surfaces of the tungsten oxide particles and the titanium oxide particles. Thereby, recombination between the electrons excited in the conduction band by light irradiation and the holes generated in the valence band is suppressed, and the photocatalytic activity of the titanium oxide-coated tungsten oxide particles can be further increased.
The electron-withdrawing substance is a compound that is supported on the surface of a photocatalyst (that is, titanium oxide particles and tungsten oxide particles) and can exhibit electron-withdrawing properties. The electron-withdrawing substance precursor is a photocatalyst. A compound that can transition to an electron-withdrawing substance on the surface of the body (for example, a compound that can be reduced to an electron-withdrawing substance by light irradiation).
電子吸引性物質またはその前駆体は、Ｃｕ、Ｐｔ、Ａｕ、Ｐｄ、Ａｇ、Ｆｅ、Ｎｂ、Ｒｕ、Ｉｒ、ＲｈおよびＣｏから選ばれる少なくとも１種の金属原子を含有してなるものであることが好ましい。より好ましくは、Ｃｕ、Ｐｔ、ＡｕおよびＰｄのうちの１種以上の金属原子を含有してなるものである。 The electron-withdrawing substance or a precursor thereof contains at least one metal atom selected from Cu, Pt, Au, Pd, Ag, Fe, Nb, Ru, Ir, Rh, and Co. preferable. More preferably, it contains one or more metal atoms of Cu, Pt, Au and Pd.
電子吸引性物質としては、例えば、前記金属原子からなる金属が挙げられ、その具体例としては、Ｃｕ、Ｐｔ、Ａｕ、Ｐｄ、Ａｇ、Ｆｅ、Ｎｂ、Ｒｕ、Ｉｒ、ＲｈおよびＣｏが挙げられる。 Examples of the electron-withdrawing substance include metals composed of the metal atoms, and specific examples thereof include Cu, Pt, Au, Pd, Ag, Fe, Nb, Ru, Ir, Rh, and Co.
電子吸引性物質の前駆体としては、例えば、前記金属原子からなる金属の水酸化物、硝酸塩、硫酸塩、ハロゲン化物、有機酸塩、炭酸塩、りん酸塩等が挙げられ、その具体例としては、Ｃｕを含む前駆体として、硝酸銅〔Ｃｕ(ＮＯ3)2〕、硫酸銅〔Ｃｕ(ＳＯ4)2〕、塩化銅〔ＣｕＣｌ2、ＣｕＣｌ〕、臭化銅〔ＣｕＢｒ2、ＣｕＢｒ〕、沃化銅〔ＣｕＩ〕、沃素酸銅〔ＣｕＩ2Ｏ6〕、塩化アンモニウム銅〔Ｃｕ(ＮＨ4)2Ｃｌ4〕、オキシ塩化銅〔Ｃｕ2Ｃｌ(ＯＨ)3〕、酢酸銅〔ＣＨ3ＣＯＯＣｕ、(ＣＨ3ＣＯＯ)2Ｃｕ〕、蟻酸銅〔(ＨＣＯＯ)2Ｃｕ〕、炭酸銅〔ＣｕＣＯ3〕、蓚酸銅〔ＣｕＣ2Ｏ4〕、クエン酸銅〔Ｃｕ2Ｃ6Ｈ4Ｏ7〕、リン酸銅〔ＣｕＰＯ4〕等；Ｐｔを含む前駆体として、塩化白金〔ＰｔＣｌ2、ＰｔＣｌ4〕、臭化白金〔ＰｔＢｒ2、ＰｔＢｒ4〕、沃化白金〔ＰｔＩ2、ＰｔＩ4〕、テトラクロロ白金酸カリウム〔Ｋ2(ＰｔＣｌ4)〕、ヘキサクロロ白金酸〔Ｈ2ＰｔＣｌ6〕、亜硫酸白金〔Ｈ3Ｐｔ(ＳＯ3)2ＯＨ〕、酸化白金〔ＰｔＯ2〕、塩化テトラアンミン白金〔Ｐｔ(ＮＨ3)4Ｃｌ2〕、炭酸水素テトラアンミン白金〔Ｃ2Ｈ14Ｎ4Ｏ6Ｐｔ〕、テトラアンミン白金リン酸水素〔Ｐｔ(ＮＨ3)4ＨＰＯ4〕、水酸化テトラアンミン白金〔Ｐｔ(ＮＨ3)4(ＯＨ)2〕、硝酸テトラアンミン白金〔Ｐｔ(ＮＯ3)2(ＮＨ3)4〕、テトラアンミン白金テトラクロロ白金〔(Ｐｔ(ＮＨ3)4)(ＰｔＣｌ4)〕、ジニトロジアミン白金〔Ｐｔ(ＮＯ2)2(ＮＨ3)2〕等；Ａｕを含む前駆体として、塩化金〔ＡｕＣｌ〕、臭化金〔ＡｕＢｒ〕、沃化金〔ＡｕＩ〕、水酸化金〔Ａｕ(ＯＨ)2〕、テトラクロロ金酸〔ＨＡｕＣｌ4〕、テトラクロロ金酸カリウム〔ＫＡｕＣｌ4〕、テトラブロモ金酸カリウム〔ＫＡｕＢｒ4〕、酸化金〔Ａｕ2Ｏ3〕等；Ｐｄを含む前駆体として、酢酸パラジウム〔(ＣＨ3ＣＯＯ)2Ｐｄ〕、塩化パラジウム〔ＰｄＣｌ2〕、臭化パラジウム〔ＰｄＢｒ2〕、沃化パラジウム〔ＰｄＩ2〕、水酸化パラジウム〔Ｐｄ(ＯＨ)2〕、硝酸パラジウム〔Ｐｄ(ＮＯ3)2〕、酸化パラジウム〔ＰｄＯ〕、硫酸パラジウム〔ＰｄＳＯ4〕、テトラクロロパラジウム酸カリウム〔Ｋ2(ＰｄＣｌ4)〕、テトラブロモパラジウム酸カリウム〔Ｋ2(ＰｄＢｒ4)〕等がそれぞれ挙げられる。なお、電子吸引性物質またはその前駆体は、それぞれ単独で用いてもよいし、２種以上を併用してもよい。また、１種以上の電子吸引性物質と１種以上の前駆体とを併用してもよいことは勿論である。 Examples of the electron-withdrawing substance precursor include metal hydroxides, nitrates, sulfates, halides, organic acid salts, carbonates, and phosphates of the above metal atoms, and specific examples thereof. As a precursor containing Cu, copper nitrate [Cu (NO 3 ) 2 ], copper sulfate [Cu (SO 4 ) 2 ], copper chloride [CuCl 2 , CuCl], copper bromide [CuBr 2 , CuBr], Copper iodide [CuI], copper iodate [CuI 2 O 6 ], ammonium chloride [Cu (NH 4 ) 2 Cl 4 ], copper oxychloride [Cu 2 Cl (OH) 3 ], copper acetate [CH 3 COOCu , (CH 3 COO) 2 Cu], copper formate [(HCOO) 2 Cu], copper carbonate [CuCO 3 ], copper oxalate [CuC 2 O 4 ], copper citrate [Cu 2 C 6 H 4 O 7 ], like copper phosphate [CuPO 4]; as a precursor containing Pt, platinum chloride [PtCl 2, PtCl 4 , Platinum bromide [PtBr 2, PtBr 4], iodide platinum [PtI 2, PtI 4], potassium tetrachloroplatinate [K 2 (PtCl 4)], hexachloroplatinic acid [H 2 PtCl 6], platinum sulfite [ H 3 Pt (SO 3) 2 OH ], platinum oxide [PtO 2], tetraammine platinum chloride [Pt (NH 3) 4 Cl 2], bicarbonate tetraammineplatinum [C 2 H 14 N 4 O 6 Pt ], tetraammine platinum Hydrogen phosphate [Pt (NH 3 ) 4 HPO 4 ], tetraammineplatinum hydroxide [Pt (NH 3 ) 4 (OH) 2 ], tetraammineplatinum nitrate [Pt (NO 3 ) 2 (NH 3 ) 4 ], tetraammine platinum Tetrachloroplatinum [(Pt (NH 3 ) 4 ) (PtCl 4 )], dinitrodiamine platinum [Pt (NO 2 ) 2 (NH 3 ) 2 ], etc .; as a precursor containing Au, gold chloride [AuCl], odor Gold [AuBr], gold iodide [Au ], Gold hydroxide [Au (OH) 2], tetrachloro aurate [HAuCl 4], potassium tetrachloro aurate [KAuCl 4], tetrabromophthalic gold potassium [KAuBr 4], gold oxide [Au 2 O 3] and the like As a precursor containing Pd, palladium acetate [(CH 3 COO) 2 Pd], palladium chloride [PdCl 2 ], palladium bromide [PdBr 2 ], palladium iodide [PdI 2 ], palladium hydroxide [Pd (OH ) 2 ], palladium nitrate [Pd (NO 3 ) 2 ], palladium oxide [PdO], palladium sulfate [PdSO 4 ], potassium tetrachloropalladate [K 2 (PdCl 4 )], potassium tetrabromopalladate [K 2 (PdBr 4 )] and the like. In addition, an electron withdrawing substance or its precursor may each be used independently, and may use 2 or more types together. Needless to say, one or more electron-withdrawing substances and one or more precursors may be used in combination.
電子吸引性物質およびその前駆体の少なくとも一方を担持させるにあたり、その担持量（使用量）は、金属原子換算で、酸化タングステン粒子１００質量部に対して、通常０．００５〜０．６質量部、好ましくは０．０１〜０．４質量部であるのがよい。担持量が０．００５質量部未満であると、得られる光触媒体の電子吸引性物質による光触媒活性の向上効果が充分に得られないおそれがあり、一方、担持量が０．６質量部を超えると、却って得られる光触媒体の光触媒作用が、担持する前のそれより低下するおそれがある。 In supporting at least one of the electron-withdrawing substance and its precursor, the supported amount (used amount) is usually 0.005 to 0.6 parts by mass with respect to 100 parts by mass of tungsten oxide particles in terms of metal atoms. The amount is preferably 0.01 to 0.4 parts by mass. If the supported amount is less than 0.005 parts by mass, the effect of improving the photocatalytic activity by the electron-withdrawing substance of the obtained photocatalyst may not be sufficiently obtained, while the supported amount exceeds 0.6 parts by mass. And there exists a possibility that the photocatalytic action of the photocatalyst body obtained on the contrary may fall from that before carrying | supporting.
電子吸引性物質およびその前駆体の少なくとも一方を酸化タングステン粒子および酸化チタン粒子の表面の少なくとも一方に担持させるには、例えば、酸化チタンで被覆した酸化タングステン粒子を水やアルコール等の適当な分散媒に分散させた後、得られた分散液の中に電子吸引性物質および／またはその前駆体を加えればよい。
また、その際、電子吸引性物質の前駆体を添加する場合には、該前駆体を電子吸引性物質に変換するために、必要に応じてその添加後に光照射を行ってもよい。
酸化タングステン粒子や酸化チタン粒子に光励起できる波長の光を照射することにより、光励起によって生成した電子によって前駆体が還元されて電子吸引性物質となり、酸化タングステン粒子および／または酸化チタン粒子の表面に担持される。
このとき、光照射で照射する光は、酸化タングステン粒子や酸化チタン粒子を光励起できる波長を有するものであれば、特に制限はなく、可視光線でもよいし、紫外線でもよい。この光照射は、前記前駆体の添加後であれば、どの段階で行なってもよい。なお、前記前駆体を添加し、その添加後に光照射を行わない場合であっても、得られる光触媒体を実際に使用する際に（光触媒体に光触媒作用を発現させる際に）光が照射されると、その時点で電子吸引性物質へ変換されることになる。
また、電子吸引性物質の前駆体を添加する場合には、より効率よく電子吸引性物質を得る目的で、光照射の前に、本発明の効果を損なわない範囲で、適宜、メタノールやエタノールや蓚酸等を加えることもできる。
In order to support at least one of the electron-withdrawing substance and its precursor on at least one of the surfaces of the tungsten oxide particles and the titanium oxide particles, for example, the tungsten oxide particles coated with titanium oxide are mixed with an appropriate dispersion medium such as water or alcohol. Then, an electron-withdrawing substance and / or a precursor thereof may be added to the obtained dispersion.
At that time, when a precursor of an electron-withdrawing substance is added, light irradiation may be performed after the addition as necessary in order to convert the precursor into an electron-withdrawing substance.
By irradiating tungsten oxide particles and titanium oxide particles with light that can be photoexcited, the precursor is reduced by the electrons generated by photoexcitation to become an electron withdrawing substance, and is supported on the surface of tungsten oxide particles and / or titanium oxide particles. Is done.
At this time, the light irradiated by the light irradiation is not particularly limited as long as it has a wavelength capable of photoexciting the tungsten oxide particles and the titanium oxide particles, and may be visible light or ultraviolet light. This light irradiation may be performed at any stage after the addition of the precursor. Even when the precursor is added and light irradiation is not performed after the addition, light is irradiated when the obtained photocatalyst is actually used (when the photocatalyst is allowed to exhibit photocatalysis). Then, at that time, it is converted into an electron-withdrawing substance.
In addition, in the case of adding an electron-withdrawing substance precursor, for the purpose of obtaining an electron-withdrawing substance more efficiently, methanol, ethanol, Succinic acid or the like can also be added.
本発明の光触媒体は、例えば、本発明の光触媒体を微粒子状の粉末の形態で使用してもよいし、分散媒中に本発明の光触媒体を分散させて、光触媒体分散液の形態で使用してもよい。
粉末を混合する際の混合方法や、分散媒中に本発明の光触媒体を分散させる際の分散方法は、それぞれ従来公知の方法から適宜採用すればよく、例えば、分散方法としては、媒体撹拌式分散機を用いる方法などが挙げられる。
The photocatalyst of the present invention may be used, for example, in the form of a fine particle powder, or the photocatalyst of the present invention may be dispersed in a dispersion medium to form a photocatalyst dispersion. May be used.
The mixing method used when mixing the powder and the dispersing method used when dispersing the photocatalyst of the present invention in the dispersion medium may be appropriately selected from conventionally known methods. For example, the dispersion method may be a medium stirring type. Examples include a method using a disperser.
本発明における分散媒としては通常、水を主成分とする水性溶媒が用いられる。具体的には、水性溶媒は、水溶性有機溶媒単独であってもよいし、水単独であってもよい。また水と水溶性有機溶媒などとの混合媒体であってもよい。
水溶性有機溶媒としては、例えば、メタノール、エタノール、プロパノール、ブタノールなどの水溶性アルコール、アセトン、メチルエチルケトン、エチルセロソルブ、ブチルセロソルブ、酢酸エチル、ジエチルエーテル等が挙げられる。なお、水溶性有機溶媒は単独で用いてもよいし、２種以上を併用してもよい。
水溶性アルコールとしては通常、メタノール、エタノールまたはプロパノールが使用され、好ましくはエタノールが使用される。また、水溶性アルコールを使用する場合は、混合媒体中の水溶性アルコールの含有量が、光触媒体分散液１００質量部に対して１０〜７０質量部（質量％）であることが好ましい。また、光触媒体分散液の乾燥特性などを考慮して、好ましくは２５〜６０質量部（質量％）であることが好ましい。
As the dispersion medium in the present invention, an aqueous solvent mainly containing water is usually used. Specifically, the aqueous solvent may be a water-soluble organic solvent alone or water alone. Further, it may be a mixed medium of water and a water-soluble organic solvent.
Examples of the water-soluble organic solvent include water-soluble alcohols such as methanol, ethanol, propanol, and butanol, acetone, methyl ethyl ketone, ethyl cellosolve, butyl cellosolve, ethyl acetate, and diethyl ether. In addition, a water-soluble organic solvent may be used independently and may use 2 or more types together.
As the water-soluble alcohol, methanol, ethanol or propanol is usually used, and ethanol is preferably used. Moreover, when using water-soluble alcohol, it is preferable that content of the water-soluble alcohol in a mixed medium is 10-70 mass parts (mass%) with respect to 100 mass parts of photocatalyst body dispersion liquids. In consideration of the drying characteristics of the photocatalyst dispersion, the amount is preferably 25 to 60 parts by mass (% by mass).
光触媒体分散液は、本発明の光触媒体と分散媒とを少なくとも含み、本発明の光触媒体の光触媒活性を大幅に損なわない範囲で、従来公知の各種添加剤を含んでいてもよい。なお、添加剤は、１種のみであってもよいし、２種以上であってもよい。
添加剤としては、例えば、光触媒作用を向上させる目的で添加されるものが挙げられる。このような光触媒作用向上効果を目的とした添加剤としては、具体的には、非晶質シリカ、シリカゾル、水ガラス、オルガノポリシロキサンなどの珪素化合物；非晶質アルミナ、アルミナゾル、水酸化アルミニウムなどのアルミニウム化合物；ゼオライト、カオリナイトのようなアルミノ珪酸塩；酸化マグネシウム、酸化カルシウム、酸化ストロンチウム、酸化バリウム、水酸化マグネシウム、水酸化カルシウム、水酸化ストロンチウム、水酸化バリウムなどのアルカリ土類金属酸化物またはアルカリ土類金属水酸化物；リン酸カルシウム、モレキュラーシーブ、活性炭、有機ポリシロキサン化合物の重縮合物、リン酸塩、フッ素系ポリマー、シリコン系ポリマー、アクリル樹脂、ポリエステル樹脂、メラミン樹脂、ウレタン樹脂、アルキド樹脂等が挙げられる。
The photocatalyst dispersion liquid contains at least the photocatalyst of the present invention and a dispersion medium, and may contain various conventionally known additives as long as the photocatalytic activity of the photocatalyst of the present invention is not significantly impaired. In addition, only 1 type may be sufficient as an additive, and 2 or more types may be sufficient as it.
Examples of the additive include those added for the purpose of improving the photocatalytic action. Specific examples of such additives for improving the photocatalytic effect include silicon compounds such as amorphous silica, silica sol, water glass, and organopolysiloxane; amorphous alumina, alumina sol, aluminum hydroxide, and the like. Aluminosilicates such as zeolite and kaolinite; alkaline earth metal oxides such as magnesium oxide, calcium oxide, strontium oxide, barium oxide, magnesium hydroxide, calcium hydroxide, strontium hydroxide, barium hydroxide Or alkaline earth metal hydroxide; calcium phosphate, molecular sieve, activated carbon, polycondensate of organic polysiloxane compound, phosphate, fluorine polymer, silicon polymer, acrylic resin, polyester resin, melamine resin, urethane resin, alkyd Butter, and the like can be mentioned.
また、添加剤としては、本発明の光触媒体を用いて基材の表面に光触媒体層を形成する際に、酸化タングステン粒子および酸化チタン粒子をより強固に基材の表面に保持させるためのバインダー等を用いることもできる（例えば、特開平８−６７８３５号公報、特開平９−２５４３７号公報、特開平１０−１８３０６１号公報、特開平１０−１８３０６２号公報、特開平１０−１６８３４９号公報、特開平１０−２２５６５８号公報、特開平１１−１６２０号公報、特開平１１−１６６１号公報、特開２００４−０５９６８６号公報、特開２００４−１０７３８１号公報、特開２００４−２５６５９０号公報、特開２００４−３５９９０２号公報、特開２００５−１１３０２８号公報、特開２００５−２３０６６１号公報、特開２００７−１６１８２４号公報など参照）。
本発明の光触媒体に前述した添加剤を含有させる際には、例えば、酸化タングステン粒子と酸化チタン粒子とを適当な分散媒に分散させてなる分散液に対して、添加剤を加えればよい。
Moreover, as an additive, when forming the photocatalyst body layer on the surface of the substrate using the photocatalyst of the present invention, a binder for holding the tungsten oxide particles and the titanium oxide particles more firmly on the surface of the substrate. (For example, JP-A-8-67835, JP-A-9-25437, JP-A-10-183061, JP-A-10-183062, JP-A-10-168349, Japanese Unexamined Patent Application Publication Nos. 10-225658, 11-1620, 11-1661, 2004-059686, 2004-107381, 2004-256590, 2004. -359902, JP-A-2005-113028, JP-A-2005-230661, JP-A-2007-1 See, for 1824 JP).
When the above-mentioned additive is contained in the photocatalyst of the present invention, for example, the additive may be added to a dispersion obtained by dispersing tungsten oxide particles and titanium oxide particles in an appropriate dispersion medium.
本発明の光触媒体は、気相中の揮発性芳香族化合物を分解するための光触媒体である。ここで、揮発性芳香族化合物の具体例としては、ベンゼン、トルエン、キシレン、メチルベンゼン、トリメチルベンゼン、エチルベンゼン、スチレン、クロロベンゼン、ジクロロベンゼン、トリクロロベンゼン、クレゾール、アニリン等が挙げられる。なお、揮発性芳香族化合物を含む気相は、通常、大気である。 The photocatalyst of the present invention is a photocatalyst for decomposing volatile aromatic compounds in the gas phase. Here, specific examples of the volatile aromatic compound include benzene, toluene, xylene, methylbenzene, trimethylbenzene, ethylbenzene, styrene, chlorobenzene, dichlorobenzene, trichlorobenzene, cresol, aniline, and the like. The gas phase containing the volatile aromatic compound is usually the atmosphere.
本発明の光触媒機能製品は、基材の表面に、上述した本発明の光触媒体で形成された光触媒体層を備えたものである。この光触媒体層は、上述した表面を酸化チタン粒子で被覆した酸化タングステン粒子で形成され、特に揮発性芳香族化合物に対して高い光触媒活性を示すものである。
光触媒体層を形成する方法は、例えば、上述した光触媒体分散液（水やアルコール等の分散媒に表面を酸化チタン粒子で被覆した酸化タングステン粒子を分散させた分散液）を、基材（製品）の表面に塗布した後、分散媒を揮発させる方法；上述した光触媒体を真空蒸着法、スパッタリング法などの物理気相蒸着法によって基材（製品）の表面に膜を形成する方法など従来公知の成膜方法によって形成することができる。
光触媒体層を形成するにあたり、光触媒体分散液の塗布は、従来公知の方法を適宜採用して行えばよい。
光触媒体層の膜厚は、特に制限されるものではなく、通常、その用途等に応じて、数百ｎｍ〜数ｍｍまで適宜設定すればよい。また、塗布後に分散媒を揮発させる方法についても、特に制限はなく、従来公知の方法を適宜採用することができる。
The photocatalytic functional product of the present invention is provided with a photocatalyst layer formed of the above-described photocatalyst of the present invention on the surface of a substrate. This photocatalyst layer is formed of tungsten oxide particles whose surfaces are covered with titanium oxide particles, and exhibits a high photocatalytic activity particularly for volatile aromatic compounds.
The photocatalyst layer is formed by, for example, using the above-described photocatalyst dispersion liquid (dispersion liquid in which tungsten oxide particles whose surfaces are coated with titanium oxide particles in a dispersion medium such as water or alcohol) is dispersed in a base material (product And the like, a method in which the dispersion medium is volatilized after coating on the surface of the above); a method of forming a film on the surface of the substrate (product) by the above-mentioned photocatalyst by physical vapor deposition such as vacuum deposition or sputtering. The film forming method can be used.
In forming the photocatalyst layer, the photocatalyst dispersion liquid may be applied by appropriately employing a conventionally known method.
The film thickness of the photocatalyst body layer is not particularly limited, and usually may be appropriately set from several hundred nm to several mm according to the application. Moreover, there is no restriction | limiting in particular also about the method of volatilizing a dispersion medium after application | coating, A conventionally well-known method can be employ | adopted suitably.
本発明の光触媒機能製品において、光触媒体層は、基材（製品）の内表面または外表面であれば、どの部分に形成されていてもよいが、例えば、光（可視光線）が照射される面であって、かつ分解対象とする揮発性芳香族化合物が発生もしくは存在する箇所と連続または断続して空間的につながる面に形成されていることが好ましい。
なお、基材（製品）の材質は、形成される光触媒体層を実用に耐えうる強度で保持できる限り、特に制限されるものではなく、例えば、プラスチック、金属、セラミックス、木材、コンクリート、紙など、あらゆる材料からなる製品を対象にすることができる。
In the photocatalytic functional product of the present invention, the photocatalyst layer may be formed on any part as long as it is the inner surface or the outer surface of the base material (product). For example, light (visible light) is irradiated. It is preferably formed on a plane and a plane that is continuously or intermittently connected to a place where a volatile aromatic compound to be decomposed is generated or exists.
The material of the base material (product) is not particularly limited as long as the formed photocatalyst layer can be held at a strength that can be practically used. For example, plastic, metal, ceramics, wood, concrete, paper, etc. , Products made of any material can be targeted.
本発明の光触媒機能製品は、屋外においては勿論のこと、蛍光灯やナトリウムランプのような可視光源からの光しか受けない屋内環境においても、光の照射によって高い光触媒作用を示す。つまり、本発明において、光触媒作用を発揮させる際に必要とされる光は、酸化タングステン粒子や酸化チタン粒子を光励起できる波長を有するものであれば、特に制限はなく、可視光線でもよいし、紫外線でもよい。
そのときの光源としては、例えば、蛍光灯、白熱電球、ハロゲンランプ、発光ダイオード、ナトリウムランプ、太陽光などを用いることができる。したがって、光触媒体層を、例えば病院の天井材、タイル、ガラスなどに形成すると、かかる光触媒体層と接触する気相中の揮発性芳香族化合物は速やかに分解されることとなる。
The photocatalytic functional product of the present invention exhibits a high photocatalytic action when irradiated with light, not only outdoors, but also in an indoor environment receiving only light from a visible light source such as a fluorescent lamp and a sodium lamp. That is, in the present invention, the light required for exerting the photocatalytic action is not particularly limited as long as it has a wavelength capable of photoexciting the tungsten oxide particles and the titanium oxide particles, and may be visible light or ultraviolet light. But you can.
As the light source at that time, for example, a fluorescent lamp, an incandescent lamp, a halogen lamp, a light emitting diode, a sodium lamp, sunlight, or the like can be used. Therefore, when the photocatalyst layer is formed on, for example, a hospital ceiling material, tile, glass, or the like, the volatile aromatic compound in the gas phase that comes into contact with the photocatalyst layer is rapidly decomposed.
本発明の光触媒機能製品の具体例としては、天井材、タイル、ガラス、壁紙、壁材、床等の建築資材；自動車内装材（自動車用インストルメントパネル、自動車用シート、自動車用天井材）；冷蔵庫やエアコン等の家電製品；衣類やカーテン等の繊維製品などが挙げられる。 Specific examples of the photocatalytic functional product of the present invention include building materials such as ceiling materials, tiles, glass, wallpaper, wall materials and floors; automobile interior materials (automobile instrument panels, automobile seats, automobile ceiling materials); Home appliances such as refrigerators and air conditioners; textile products such as clothes and curtains.
以下、本発明を実施例によって詳細に説明するが、本発明は、かかる実施例によって限定されるものではない。
なお、実施例および比較例における各種物性の測定および得られた光触媒体の評価は以下の方法で行った。
EXAMPLES Hereinafter, although an Example demonstrates this invention in detail, this invention is not limited by this Example.
In addition, measurement of various physical properties and evaluation of the obtained photocatalyst in Examples and Comparative Examples were performed by the following methods.
＜ＢＥＴ比表面積＞
比表面積測定装置（ユアサアイオニクス（株）製「モノソーブ」）を用いて窒素吸着法にて測定した。
<BET specific surface area>
It measured by the nitrogen adsorption method using the specific surface area measuring apparatus ("monosorb" by Yuasa Ionics Co., Ltd.).
＜揮発性芳香族化合物に対する光触媒活性（トルエン分解能）＞
揮発性芳香族化合物に対する光触媒活性は、可視光照射下でＰｔ担持酸化チタン被覆酸化タングステン粒子またはＰｔ担酸化タングステン粒子（以下、光触媒体粒子と称する）の光触媒作用によるトルエンの分解反応を行い、トルエンの完全分解生成物である二酸化炭素（ＣＯ2）の生成速度を求めることにより評価した。
具体的には、内容積３３０ｍＬの密閉可能なガラス製容器の中に、１５ｍｍ×１５ｍｍの正方形に広げた光触媒体粒子５０ｍｇを設置し、上方よりキセノンランプ（Ｐｅｒｋｉｎ Ｅｌｍｅｒ社製「Ｃｅｒｍａｘ」：３００Ｗ）を用いて紫外線と可視光線の両方を含む光を３０分間照射して、光触媒体粒子表面の残存有機物を除去した。その後、ガラス製容器を密閉して、その中にシリンジを用いて９．４マイクロモルのトルエンを注入し、遮光下で２時間放置した。
次いで、紫外線カットフィルター（旭テクノガラス（株）製「Ｙ−４４」）を装着したキセノンランプを光源として可視光を照射し、光（可視光）の照射開始時から１０分間隔でガラス製容器内のガスの一部をサンプリングして、トルエンとＣＯ2の濃度をガスクロマトグラフ（アジレント・テクノロジー（株）製「Ａｇｉｌｅｎｔ３０００ マイクロＧＣ」）にて測定した。
そして、光（可視光）の照射開始時から４時間におけるトルエンの完全分解生成物であるＣＯ2の生成速度を求めた。ＣＯ2の生成速度が速いほど、トルエン分解能が高いと言える。
<Photocatalytic activity for volatile aromatic compounds (toluene resolution)>
The photocatalytic activity for volatile aromatic compounds is obtained by performing a decomposition reaction of toluene by photocatalytic action of Pt-supported titanium oxide-coated tungsten oxide particles or Pt-supported tungsten oxide particles (hereinafter referred to as photocatalyst particles) under irradiation with visible light. This was evaluated by determining the rate of formation of carbon dioxide (CO 2 ), which is a complete decomposition product of the above.
Specifically, photocatalyst particles 50 mg spread in a 15 mm × 15 mm square were placed in a sealable glass container having an internal volume of 330 mL, and a xenon lamp (“Cermax” manufactured by Perkin Elmer: 300 W) from above. Was used for 30 minutes to irradiate light containing both ultraviolet rays and visible rays to remove residual organic substances on the surface of the photocatalyst particles. Thereafter, the glass container was sealed, 9.4 micromoles of toluene was injected into it using a syringe, and left for 2 hours under light shielding.
Next, visible light is irradiated using a xenon lamp equipped with an ultraviolet cut filter (“Y-44” manufactured by Asahi Techno Glass Co., Ltd.) as a light source, and a glass container is formed at an interval of 10 minutes from the start of light (visible light) irradiation. A part of the gas was sampled, and the concentrations of toluene and CO 2 were measured with a gas chromatograph (“Agilent 3000 Micro GC” manufactured by Agilent Technologies).
The light was determined production rate of CO 2 is completely decomposed product of toluene in 4 hours from the irradiation start of the (visible light). It can be said that the higher the CO 2 production rate, the higher the toluene resolution.
（製造例１−ポリメタクリル酸メチル粒子の合成）
５Ｌガラス製反応容器に、水２５０質量部、炭酸ナトリウム１．５質量部、濃度１５質量％のドデシルベンゼンスルホン酸ナトリウム水溶液４．７質量部、およびペルオキソ二硫酸ナトリウム０．０６質量部を仕込み、攪拌しながら窒素雰囲気下８０℃にてメタクリル酸メチル６１．５質量部を６０分間かけて連続的に添加した後、さらに攪拌しながら同温度で６０分間熟成した。次いで、水１２質量部とペルオキソ二硫酸ナトリウム０．０６質量部とからなる水溶液を添加して攪拌し、その後、攪拌しながら８０℃にてメタクリル酸メチル６１．５質量部を６０分間かけて連続的に添加した後、さらに攪拌しながら同温度で６０分間熟成して、重合体のラテックスを得た。このラテックスの固形分濃度は３１質量％であった。
次に、得られた重合体のラテックスを−２０℃の冷凍庫内で２４時間凍結させた後、融解させる処理を施すことにより重合体粒子を凝集させた。得られた凝集スラリーを遠心分離機を用いて１５００ｒｐｍ（４７０Ｇ）の条件で１０分間脱水した後、得られた重合体のウエットケーキを８０℃の真空乾燥機にて２４時間乾燥させて、球状のポリメタクリル酸メチル粒子を得た。
得られたポリメタクリル酸メチル粒子の粒径を光散乱光度計（大塚電子（株）製「ＤＬＳ−７０００」）を用いて動的散乱法により測定したところ、平均粒径は１４５ｎｍであった。
(Production Example 1-Synthesis of polymethyl methacrylate particles)
A 5 L glass reaction vessel was charged with 250 parts by weight of water, 1.5 parts by weight of sodium carbonate, 4.7 parts by weight of a sodium dodecylbenzenesulfonate aqueous solution having a concentration of 15% by weight, and 0.06 parts by weight of sodium peroxodisulfate. 61.5 parts by mass of methyl methacrylate was continuously added over 60 minutes at 80 ° C. under a nitrogen atmosphere with stirring, and then aged at the same temperature for 60 minutes with further stirring. Next, an aqueous solution consisting of 12 parts by weight of water and 0.06 parts by weight of sodium peroxodisulfate was added and stirred, and then 61.5 parts by weight of methyl methacrylate was continuously added over 60 minutes at 80 ° C. with stirring. Then, the mixture was aged at the same temperature for 60 minutes with further stirring to obtain a polymer latex. The solid content concentration of this latex was 31% by mass.
Next, the obtained polymer latex was frozen in a freezer at −20 ° C. for 24 hours and then subjected to a melting treatment to aggregate the polymer particles. The obtained agglomerated slurry was dehydrated using a centrifuge at 1500 rpm (470 G) for 10 minutes, and then the resulting polymer wet cake was dried in a vacuum dryer at 80 ° C. for 24 hours to obtain spherical particles. Polymethyl methacrylate particles were obtained.
When the particle size of the obtained polymethyl methacrylate particles was measured by a dynamic scattering method using a light scattering photometer (“DLS-7000” manufactured by Otsuka Electronics Co., Ltd.), the average particle size was 145 nm.
（製造例２−酸化タングステン粒子の合成）
ＷＯ3換算での濃度５０質量％のメタタングステン酸アンモニウム水溶液（日本無機化学工業（株）製「ＭＷ−２」；比重：１．８ｇ／ｍＬ）８ｍＬにメタノール４．４ｍＬを加えてスパチュラでかるく撹拌した溶液に、製造例１で得たポリメタクリル酸メチル粒子６ｇを加えて混合した。
その後、得られた混合物を室温で３時間静置した後、吸引ろ過により固液分離し、得られた固形物をシャーレに移してドラフト内に放置することにより自然乾燥させた。得られた乾燥後の固形物２ｇを焼成炉にて５℃／分で４２０℃まで昇温し、空気中４２０℃で５時間焼成して、炭素分を燃焼除去し、酸化タングステン粒子を得た。得られた酸化タングステン粒子のＢＥＴ比表面積は２３ｍ2／ｇであった。
(Production Example 2-Synthesis of tungsten oxide particles)
WO 3 converted ammonium metatungstate aqueous solution (“MW-2” manufactured by Nippon Inorganic Chemical Industry Co., Ltd .; specific gravity: 1.8 g / mL) was added to 4.4 mL of methanol and stirred with a spatula. To the stirred solution, 6 g of the polymethyl methacrylate particles obtained in Production Example 1 were added and mixed.
Thereafter, the obtained mixture was allowed to stand at room temperature for 3 hours, and then was subjected to solid-liquid separation by suction filtration. The obtained solid was transferred to a petri dish and allowed to stand in a fume hood for natural drying. 2 g of the obtained solid matter after drying was heated to 420 ° C. at 5 ° C./min in a firing furnace, and calcined in air at 420 ° C. for 5 hours to burn and remove the carbon component to obtain tungsten oxide particles. . The obtained tungsten oxide particles had a BET specific surface area of 23 m 2 / g.
（実施例１）
製造例２で得られた酸化タングステン粒子１ｇを水５０ｍＬに分散し、１時間超音波処理を施した後、チタンラクテート（マツモトファインケミカル（株）製「オルガチックス ＴＣ−３１０」）を添加して３０分撹拌した後に、ロータリーエバポレーターを用いて、およそ５０℃に加熱しながら溶媒を除去した後、チタンラクテートで被覆した酸化タングステン粒子を得た。尚、チタンラクテートの添加量は、酸化タングステン（ＷＯ3）１００質量部に対してチタン（Ｔｉ）として５質量部であった。
その後、前記チタンラクテートで被覆した酸化タングステン粒子を４２０℃で空気中で焼成して、炭素分を燃焼除去し、酸化チタン粒子で被覆した酸化チタン被覆酸化タングステン粒子を得た。
Example 1
1 g of the tungsten oxide particles obtained in Production Example 2 was dispersed in 50 mL of water, subjected to ultrasonic treatment for 1 hour, and then added with titanium lactate (“Olgatix TC-310” manufactured by Matsumoto Fine Chemical Co., Ltd.) and added 30 After stirring for a minute, the solvent was removed while heating to about 50 ° C. using a rotary evaporator, and then tungsten oxide particles coated with titanium lactate were obtained. The amount of titanium lactate added was 5 parts by mass as titanium (Ti) with respect to 100 parts by mass of tungsten oxide (WO 3 ).
Thereafter, the tungsten oxide particles coated with the titanium lactate were fired in air at 420 ° C. to burn and remove the carbon content, thereby obtaining titanium oxide-coated tungsten oxide particles coated with the titanium oxide particles.
次に、得られた酸化チタン被覆酸化タングステン粒子０．５ｇを水５０ｍＬに分散し、そこに白金（Ｐｔ）が酸化タングステン粒子１００質量部に対して０．５質量部となるように濃度０．０１９ｍｏｌ／Ｌのヘキサクロロ白金酸水溶液（Ｈ2ＰｔＣｌ6）を入れて酸化チタン被覆酸化タングステン粒子分散液を得、アルゴンガスをこの分散液に３０分間吹き込んだ後、密閉条件下で１時間光照射を行った。光源には青色の発光ダイオード（OptoSupply Limited製、 5mmΦ Blue LED 「OSUB5111A-ST」（輝度：7000 mcd、波長：470 nm)）を２８個用いた。
光照射後、得られた分散液にメタノール５ｍＬを加えて、アルゴンガスを再度１時間吹き込んだ後、攪拌しながら上記と同様にして光の照射を１時間行った。
その後、得られた分散液を濾過、水洗浄、１２０℃で乾燥することにより、Ｐｔ担持酸化チタン被覆酸化タングステン粒子を得た。
Next, 0.5 g of the obtained titanium oxide-coated tungsten oxide particles are dispersed in 50 mL of water, and the concentration of platinum (Pt) is 0.5 parts by mass with respect to 100 parts by mass of the tungsten oxide particles. 019 mol / L hexachloroplatinic acid aqueous solution (H 2 PtCl 6 ) was added to obtain a titanium oxide-coated tungsten oxide particle dispersion, and argon gas was blown into the dispersion for 30 minutes, followed by light irradiation for 1 hour under sealed conditions. went. As the light source, 28 blue light-emitting diodes (manufactured by OptoSupply Limited, 5 mmΦ Blue LED “OSUB5111A-ST” (luminance: 7000 mcd, wavelength: 470 nm)) were used.
After light irradiation, 5 mL of methanol was added to the obtained dispersion, and argon gas was blown again for 1 hour, followed by light irradiation for 1 hour in the same manner as described above while stirring.
Thereafter, the obtained dispersion was filtered, washed with water, and dried at 120 ° C. to obtain Pt-supported titanium oxide-coated tungsten oxide particles.
このＰｔ担持酸化チタン被覆酸化タングステン粒子の光触媒活性を評価したところ、可視光照射下でのトルエンの分解反応における二酸化炭素の生成速度は０．９１μｍｏｌ／ｈであった。 When the photocatalytic activity of the Pt-supported titanium oxide-coated tungsten oxide particles was evaluated, the production rate of carbon dioxide in the decomposition reaction of toluene under irradiation with visible light was 0.91 μmol / h.
（実施例２）
チタンラクテートの添加量を、酸化タングステン（ＷＯ3）１００質量部に対してチタン（Ｔｉ）として１０質量部とした以外は、実施例１と同様にしてＰｔ担持酸化チタン被覆酸化タングステン粒子を得た。このＰｔ担持酸化チタン被覆酸化タングステン粒子の光触媒活性を評価したところ、可視光照射下でのトルエンの分解反応における二酸化炭素の生成速度は１．２５μｍｏｌ／ｈであった。
(Example 2)
Pt-supported titanium oxide-coated tungsten oxide particles were obtained in the same manner as in Example 1 except that the amount of titanium lactate was changed to 10 parts by mass as titanium (Ti) with respect to 100 parts by mass of tungsten oxide (WO 3 ). . When the photocatalytic activity of the Pt-supported titanium oxide-coated tungsten oxide particles was evaluated, the production rate of carbon dioxide in the decomposition reaction of toluene under irradiation with visible light was 1.25 μmol / h.
（実施例３）
チタンラクテートの添加量を、酸化タングステン（ＷＯ3）１００質量部に対してチタン（Ｔｉ）として２０質量部とした以外は、実施例１と同様にしてＰｔ担持酸化チタン被覆酸化タングステン粒子を得た。このＰｔ担持酸化チタン被覆酸化タングステン粒子酸化タングステン粒子の光触媒活性を評価したところ、可視光照射下でのトルエンの分解反応における二酸化炭素の生成速度は１．１７μｍｏｌ／ｈであった。
(Example 3)
Pt-supported titanium oxide-coated tungsten oxide particles were obtained in the same manner as in Example 1, except that the amount of titanium lactate was 20 parts by mass as titanium (Ti) with respect to 100 parts by mass of tungsten oxide (WO 3 ). . When the photocatalytic activity of the Pt-supported titanium oxide-coated tungsten oxide particles and tungsten oxide particles was evaluated, the carbon dioxide production rate in the decomposition reaction of toluene under visible light irradiation was 1.17 μmol / h.
（実施例４）
チタンラクテートの添加量を、酸化タングステン（ＷＯ3）１００質量部に対してチタン（Ｔｉ）として３０質量部とした以外は、実施例１と同様にしてＰｔ担持酸化チタン被覆酸化タングステン粒子を得た。このＰｔ担持酸化チタン被覆酸化タングステン粒子の光触媒活性を評価したところ、可視光照射下でのトルエンの分解反応における二酸化炭素の生成速度は０．９４μｍｏｌ／ｈであった。
Example 4
Pt-supported titanium oxide-coated tungsten oxide particles were obtained in the same manner as in Example 1 except that the amount of titanium lactate was 30 parts by mass as titanium (Ti) with respect to 100 parts by mass of tungsten oxide (WO 3 ). . When the photocatalytic activity of the Pt-supported titanium oxide-coated tungsten oxide particles was evaluated, the production rate of carbon dioxide in the decomposition reaction of toluene under irradiation with visible light was 0.94 μmol / h.
（実施例５）
チタンラクテートの添加量を、酸化タングステン（ＷＯ3）１００質量部に対してチタン（Ｔｉ）として４０質量部とした以外は、実施例１と同様にしてＰｔ担持酸化チタン被覆酸化タングステン粒子を得た。このＰｔ担持酸化チタン被覆酸化タングステン粒子の光触媒活性を評価したところ、可視光照射下でのトルエンの分解反応における二酸化炭素の生成速度は１．０１μｍｏｌ／ｈであった。
(Example 5)
Pt-supported titanium oxide-coated tungsten oxide particles were obtained in the same manner as in Example 1 except that the amount of titanium lactate was 40 parts by mass as titanium (Ti) with respect to 100 parts by mass of tungsten oxide (WO 3 ). . When the photocatalytic activity of the Pt-supported titanium oxide-coated tungsten oxide particles was evaluated, the production rate of carbon dioxide in the decomposition reaction of toluene under visible light irradiation was 1.01 μmol / h.
（実施例６）
チタンラクテートで被覆された酸化タングステン粒子を、３００℃で空気中で焼成した以外は実施例２と同様にしてＰｔ担持酸化チタン被覆酸化タングステン粒子を得た。このＰｔ担持酸化チタン被覆酸化タングステン粒子の光触媒活性を評価したところ、可視光照射下でのトルエンの分解反応における二酸化炭素の生成速度は０．８９μｍｏｌ／ｈであった。
(Example 6)
Pt-supported titanium oxide-coated tungsten oxide particles were obtained in the same manner as in Example 2 except that the tungsten oxide particles coated with titanium lactate were fired in air at 300 ° C. When the photocatalytic activity of the Pt-supported titanium oxide-coated tungsten oxide particles was evaluated, the carbon dioxide production rate in the decomposition reaction of toluene under visible light irradiation was 0.89 μmol / h.
（実施例７）
チタンラクテートで被覆された酸化タングステン粒子を、３５０℃で空気中で焼成した以外は実施例２と同様にしてＰｔ担持酸化チタン被覆酸化タングステン粒子を得た。このＰｔ担持酸化チタン被覆酸化タングステン粒子の光触媒活性を評価したところ、可視光照射下でのトルエンの分解反応における二酸化炭素の生成速度は０．９６μｍｏｌ／ｈであった。
(Example 7)
Pt-supported titanium oxide-coated tungsten oxide particles were obtained in the same manner as in Example 2 except that the tungsten oxide particles coated with titanium lactate were fired in air at 350 ° C. When the photocatalytic activity of the Pt-supported titanium oxide-coated tungsten oxide particles was evaluated, the production rate of carbon dioxide in the decomposition reaction of toluene under irradiation with visible light was 0.96 μmol / h.
（実施例８）
チタンラクテートで被覆された酸化タングステン粒子を、５００℃で空気中で焼成した以外は実施例２と同様にしてＰｔ担持酸化チタン被覆酸化タングステン粒子を得た。このＰｔ担持酸化チタン被覆酸化タングステン粒子の光触媒活性を評価したところ、可視光照射下でのトルエンの分解反応における二酸化炭素の生成速度は１．０４μｍｏｌ／ｈであった。
(Example 8)
Pt-supported titanium oxide-coated tungsten oxide particles were obtained in the same manner as in Example 2 except that the tungsten oxide particles coated with titanium lactate were fired in air at 500 ° C. When the photocatalytic activity of the Pt-supported titanium oxide-coated tungsten oxide particles was evaluated, the production rate of carbon dioxide in the decomposition reaction of toluene under irradiation with visible light was 1.04 μmol / h.
（実施例９）
チタンラクテートで被覆された酸化タングステン粒子を、５５０℃で空気中で焼成した以外は実施例２と同様にしてＰｔ担持酸化チタン被覆酸化タングステン粒子を得た。このＰｔ担持酸化チタン被覆酸化タングステン粒子の光触媒活性を評価したところ、可視光照射下でのトルエンの分解反応における二酸化炭素の生成速度は１．０８μｍｏｌ／ｈであった。
Example 9
Pt-supported titanium oxide-coated tungsten oxide particles were obtained in the same manner as in Example 2 except that the tungsten oxide particles coated with titanium lactate were fired in air at 550 ° C. When the photocatalytic activity of the Pt-supported titanium oxide-coated tungsten oxide particles was evaluated, the production rate of carbon dioxide in the decomposition reaction of toluene under visible light irradiation was 1.08 μmol / h.
（比較例1）
製造例２で得られた酸化タングステン粒子０．５ｇを水５０ｍＬに分散し、そこに白金（Ｐｔ）が酸化タングステン粒子１００質量部に対して０．５質量部となるように濃度０．０１９ｍｏｌ／Ｌのヘキサクロロ白金酸水溶液（Ｈ2ＰｔＣｌ6）を入れて酸化タングステン粒子分散液を得、アルゴンガスをこの分散液に３０分間吹き込んだ後、密閉条件下で１時間光照射を行った。光源には紫色の発光ダイオード（OptoSupply Limited製、5mmΦ Blue LED 「OSUB5111A-ST」(輝度：7000mcd、波長：470nm)）を２８個用いた。
光照射後、得られた分散液にメタノール５ｍＬを加えて、アルゴンガスを再度１時間吹き込んだ後、攪拌しながら上記と同様にして光の照射を１時間行った。
その後、得られた分散液を濾過、水洗浄、１２０℃で乾燥することにより、Ｐｔ担持酸化タングステン粒子を得た。
(Comparative Example 1)
0.5 g of tungsten oxide particles obtained in Production Example 2 was dispersed in 50 mL of water, and the concentration was 0.019 mol / wt so that platinum (Pt) was 0.5 parts by mass with respect to 100 parts by mass of tungsten oxide particles. An aqueous solution of hexachloroplatinic acid L (H 2 PtCl 6 ) was added to obtain a tungsten oxide particle dispersion, and argon gas was blown into the dispersion for 30 minutes, followed by light irradiation for 1 hour under sealed conditions. Twenty-eight purple light-emitting diodes (manufactured by OptoSupply Limited, 5 mmφ Blue LED “OSUB5111A-ST” (luminance: 7000 mcd, wavelength: 470 nm)) were used as the light source.
After light irradiation, 5 mL of methanol was added to the obtained dispersion, and argon gas was blown again for 1 hour, followed by light irradiation for 1 hour in the same manner as described above while stirring.
Thereafter, the obtained dispersion was filtered, washed with water, and dried at 120 ° C. to obtain Pt-supported tungsten oxide particles.
このＰｔ担酸化タングステン粒子の光触媒活性を評価したところ、可視光照射下でのトルエンの分解反応における二酸化炭素の生成速度は０．５６μｍｏｌ／ｈであった。 When the photocatalytic activity of the Pt-supported tungsten oxide particles was evaluated, the carbon dioxide production rate in the decomposition reaction of toluene under visible light irradiation was 0.56 μmol / h.
（比較例２）
チタンラクテートの添加量を、酸化タングステン（ＷＯ3）１００質量部に対してチタン（Ｔｉ）として５０質量部とした以外は、実施例１と同様にしてＰｔ担持酸化チタン被覆酸化タングステン粒子酸化タングステン粒子を得た。このＰｔ担持酸化チタン被覆酸化タングステン粒子の光触媒活性を評価したところ、可視光照射下でのトルエンの分解反応における二酸化炭素の生成速度は０．７１μｍｏｌ／ｈであった。
(Comparative Example 2)
Pt-supported titanium oxide-coated tungsten oxide particles Tungsten oxide particles in the same manner as in Example 1 except that the amount of titanium lactate was changed to 50 parts by mass as titanium (Ti) with respect to 100 parts by mass of tungsten oxide (WO 3 ). Got. When the photocatalytic activity of the Pt-supported titanium oxide-coated tungsten oxide particles was evaluated, the production rate of carbon dioxide in the decomposition reaction of toluene under visible light irradiation was 0.71 μmol / h.
実施例１〜９と比較例１及び２を比べると、酸化タングステン粒子を単独で用いるよりも、酸化チタン粒子を最適量被覆した酸化チタン被覆酸化タングステン粒子を用いる方が、優れたトルエン分解能を示すことが明らかである。 Comparing Examples 1 to 9 with Comparative Examples 1 and 2, the use of titanium oxide-coated tungsten oxide particles coated with an optimal amount of titanium oxide particles shows better toluene resolution than the use of tungsten oxide particles alone. It is clear.
（参考例１）
実施例１〜９で得たＰｔ担持酸化チタン被覆酸化タングステン粒子を水やアルコール等の有機溶媒中に分散させて分散液を得、この分散液を天井を構成する天井材の表面に塗布し乾燥させることにより、天井材の表面に光触媒体層を形成することができ、これによって、屋内照明による光照射により屋内の空気中に含まれるトルエンなどの揮発性芳香族化合物濃度を低減することができる。
(Reference Example 1)
The Pt-supported titanium oxide-coated tungsten oxide particles obtained in Examples 1 to 9 were dispersed in an organic solvent such as water or alcohol to obtain a dispersion, and this dispersion was applied to the surface of the ceiling material constituting the ceiling and dried. By doing so, a photocatalyst layer can be formed on the surface of the ceiling material, whereby the concentration of volatile aromatic compounds such as toluene contained in indoor air can be reduced by light irradiation by indoor lighting. .
（参考例２）
実施例１〜９で得たＰｔ担持酸化チタン被覆酸化タングステン粒子を水やアルコール等の有機溶媒中に分散させて分散液を得、この分散液を屋内の壁面に施工されたタイルに塗布し乾燥させることにより、このタイル表面に光触媒体層を形成することができ、これによって、屋内照明による光照射により屋内の空気中に含まれるトルエンなどの揮発性芳香族化合物濃度を低減することができる。
(Reference Example 2)
The Pt-supported titanium oxide-coated tungsten oxide particles obtained in Examples 1 to 9 were dispersed in an organic solvent such as water or alcohol to obtain a dispersion, and this dispersion was applied to a tile constructed on an indoor wall surface and dried. By doing so, a photocatalyst layer can be formed on the surface of the tile, whereby the concentration of volatile aromatic compounds such as toluene contained in indoor air can be reduced by light irradiation by indoor lighting.
（参考例３）
実施例１〜９で得たＰｔ担持酸化チタン被覆酸化タングステン粒子を水やアルコール等の有機溶媒中に分散させて分散液を得、この分散液を窓ガラスの屋内側表面に塗布し乾燥させることにより、このガラス表面に光触媒体層を形成することができ、これによって、屋内照明による光照射により屋内の空気中に含まれるトルエンなどの揮発性芳香族化合物濃度を低減することができる。
(Reference Example 3)
Disperse the Pt-supported titanium oxide-coated tungsten oxide particles obtained in Examples 1 to 9 in an organic solvent such as water or alcohol to obtain a dispersion, and apply the dispersion to the indoor side surface of the window glass and dry it. Thus, a photocatalyst layer can be formed on the glass surface, whereby the concentration of volatile aromatic compounds such as toluene contained in indoor air can be reduced by light irradiation by indoor lighting.
（参考例４）
実施例１〜９で得たＰｔ担持酸化チタン被覆酸化タングステン粒子を水やアルコール等の有機溶媒中に分散させて分散液を得、この分散液を壁紙に塗布し乾燥させることにより、この壁紙の表面に光触媒体層を形成することができ、さらにこの壁紙を屋内の壁面に施工することによって、屋内照明による光照射により屋内の空気中に含まれるトルエンなどの揮発性芳香族化合物の濃度を低減することができる。
(Reference Example 4)
The Pt-supported titanium oxide-coated tungsten oxide particles obtained in Examples 1 to 9 were dispersed in an organic solvent such as water or alcohol to obtain a dispersion, and this dispersion was applied to wallpaper and dried to obtain a wallpaper. A photocatalyst layer can be formed on the surface, and by installing this wallpaper on the indoor wall surface, the concentration of volatile aromatic compounds such as toluene contained in indoor air is reduced by light irradiation by indoor lighting. can do.
（参考例５）
実施例１〜９で得たＰｔ担持酸化チタン被覆酸化タングステン粒子を水やアルコール等の有機溶媒中に分散させて分散液を得、この分散液を自動車用インストルメントパネル、自動車用シート、自動車の天井材などの自動車内装材の表面に塗布し乾燥させることにより、これら自動車内装材の表面に光触媒体層を形成することができ、これによって、車内照明による光照射により車内の空気中に含まれるトルエンなどの揮発性芳香族化合物の濃度を低減することができる。
(Reference Example 5)
The Pt-supported titanium oxide-coated tungsten oxide particles obtained in Examples 1 to 9 were dispersed in an organic solvent such as water or alcohol to obtain a dispersion, and this dispersion was used for an automobile instrument panel, an automobile seat, an automobile. A photocatalyst layer can be formed on the surface of these automobile interior materials by applying to the surface of the interior materials of the automobile such as ceiling materials and drying, thereby being included in the air in the vehicle by light irradiation by the interior lighting. The concentration of volatile aromatic compounds such as toluene can be reduced.
（参考例６）
実施例１〜９で得たＰｔ担持酸化チタン被覆酸化タングステン粒子を水やアルコール等の有機溶媒中に分散させて分散液を得、この分散液を屋内の床面に塗布し乾燥させることにより、この床面に光触媒体層を形成することができ、これによって、屋内照明による光照射により屋内の空気中に含まれるトルエンなどの揮発性芳香族化合物の濃度を低減することができる。
(Reference Example 6)
By dispersing the Pt-supported titanium oxide-coated tungsten oxide particles obtained in Examples 1 to 9 in an organic solvent such as water or alcohol to obtain a dispersion, and applying this dispersion to an indoor floor surface and drying, A photocatalyst layer can be formed on the floor surface, whereby the concentration of volatile aromatic compounds such as toluene contained in indoor air can be reduced by light irradiation by indoor lighting.
（参考例７）
実施例１〜９で得たＰｔ担持酸化チタン被覆酸化タングステン粒子を水やアルコール等の有機溶媒中に分散させて分散液を得、この分散液を衣類やカーテン等の繊維製品に塗布し乾燥させることにより、この繊維製品に光触媒体層を形成することができ、これによって、屋内照明による光照射により屋内の空気中に含まれるトルエンなどの揮発性芳香族化合物の濃度を低減することができる。
(Reference Example 7)
The Pt-supported titanium oxide-coated tungsten oxide particles obtained in Examples 1 to 9 are dispersed in an organic solvent such as water or alcohol to obtain a dispersion, and this dispersion is applied to textiles such as clothing and curtains and dried. As a result, a photocatalyst layer can be formed on the fiber product, whereby the concentration of volatile aromatic compounds such as toluene contained in indoor air can be reduced by light irradiation by indoor lighting.
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| JP2016059894A (en) * | 2014-09-19 | 2016-04-25 | シャープ株式会社 | Photocatalytic material |
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