JP2008284411A - Photocatalyst included in hollow porous shell layer and its manufacturing method - Google Patents
Photocatalyst included in hollow porous shell layer and its manufacturing method Download PDFInfo
- Publication number
- JP2008284411A JP2008284411A JP2007128851A JP2007128851A JP2008284411A JP 2008284411 A JP2008284411 A JP 2008284411A JP 2007128851 A JP2007128851 A JP 2007128851A JP 2007128851 A JP2007128851 A JP 2007128851A JP 2008284411 A JP2008284411 A JP 2008284411A
- Authority
- JP
- Japan
- Prior art keywords
- photocatalyst
- layer
- group
- pore
- porous shell
- 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
Links
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 238
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 41
- 239000002245 particle Substances 0.000 claims abstract description 87
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 81
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 80
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 75
- 238000000576 coating method Methods 0.000 claims abstract description 44
- 239000011248 coating agent Substances 0.000 claims abstract description 42
- 230000001699 photocatalysis Effects 0.000 claims abstract description 39
- 239000002904 solvent Substances 0.000 claims abstract description 31
- 239000002243 precursor Substances 0.000 claims abstract description 28
- 239000011148 porous material Substances 0.000 claims description 86
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 55
- -1 alkali metal titanate Chemical class 0.000 claims description 37
- 238000000034 method Methods 0.000 claims description 33
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 30
- 229910052751 metal Inorganic materials 0.000 claims description 23
- 239000002184 metal Substances 0.000 claims description 23
- 238000001179 sorption measurement Methods 0.000 claims description 21
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 17
- 239000004094 surface-active agent Substances 0.000 claims description 16
- 229910052757 nitrogen Inorganic materials 0.000 claims description 15
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical group [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 14
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 14
- 125000000524 functional group Chemical group 0.000 claims description 12
- 229920003169 water-soluble polymer Polymers 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 11
- 238000002156 mixing Methods 0.000 claims description 11
- 239000012756 surface treatment agent Substances 0.000 claims description 11
- 150000004703 alkoxides Chemical class 0.000 claims description 10
- 238000002360 preparation method Methods 0.000 claims description 10
- 230000008569 process Effects 0.000 claims description 10
- 239000000693 micelle Substances 0.000 claims description 9
- 239000000123 paper Substances 0.000 claims description 9
- 239000000835 fiber Substances 0.000 claims description 8
- 239000004033 plastic Substances 0.000 claims description 7
- 229920003023 plastic Polymers 0.000 claims description 7
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 7
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 6
- 125000000217 alkyl group Chemical group 0.000 claims description 6
- XPFVYQJUAUNWIW-UHFFFAOYSA-N furfuryl alcohol Chemical compound OCC1=CC=CO1 XPFVYQJUAUNWIW-UHFFFAOYSA-N 0.000 claims description 6
- 229910052710 silicon Inorganic materials 0.000 claims description 6
- 239000010703 silicon Substances 0.000 claims description 6
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 5
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 4
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 4
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 4
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 claims description 4
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 4
- 229910052783 alkali metal Inorganic materials 0.000 claims description 4
- 239000008103 glucose Substances 0.000 claims description 4
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 claims description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 4
- 229910052782 aluminium Inorganic materials 0.000 claims description 3
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 claims description 3
- 229910001960 metal nitrate Inorganic materials 0.000 claims description 3
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 claims description 3
- 229910052697 platinum Inorganic materials 0.000 claims description 3
- 229910001930 tungsten oxide Inorganic materials 0.000 claims description 3
- DMKKMGYBLFUGTO-UHFFFAOYSA-N 2-methyloxirane;oxirane Chemical compound C1CO1.C1CO1.CC1CO1 DMKKMGYBLFUGTO-UHFFFAOYSA-N 0.000 claims description 2
- 125000006325 2-propenyl amino group Chemical group [H]C([H])=C([H])C([H])([H])N([H])* 0.000 claims description 2
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 claims description 2
- 229910052684 Cerium Inorganic materials 0.000 claims description 2
- CXRFDZFCGOPDTD-UHFFFAOYSA-M Cetrimide Chemical compound [Br-].CCCCCCCCCCCCCC[N+](C)(C)C CXRFDZFCGOPDTD-UHFFFAOYSA-M 0.000 claims description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 2
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims description 2
- 239000005751 Copper oxide Substances 0.000 claims description 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 2
- 229920002873 Polyethylenimine Polymers 0.000 claims description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 2
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 2
- 229920002125 Sokalan® Polymers 0.000 claims description 2
- VBIIFPGSPJYLRR-UHFFFAOYSA-M Stearyltrimethylammonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCCCC[N+](C)(C)C VBIIFPGSPJYLRR-UHFFFAOYSA-M 0.000 claims description 2
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 claims description 2
- 229930006000 Sucrose Natural products 0.000 claims description 2
- 150000001340 alkali metals Chemical class 0.000 claims description 2
- 125000004103 aminoalkyl group Chemical group 0.000 claims description 2
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 claims description 2
- 229910000416 bismuth oxide Inorganic materials 0.000 claims description 2
- 229910000420 cerium oxide Inorganic materials 0.000 claims description 2
- WOWHHFRSBJGXCM-UHFFFAOYSA-M cetyltrimethylammonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCC[N+](C)(C)C WOWHHFRSBJGXCM-UHFFFAOYSA-M 0.000 claims description 2
- 125000004965 chloroalkyl group Chemical group 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 239000010949 copper Substances 0.000 claims description 2
- 229910000431 copper oxide Inorganic materials 0.000 claims description 2
- 125000004966 cyanoalkyl group Chemical group 0.000 claims description 2
- HXWGXXDEYMNGCT-UHFFFAOYSA-M decyl(trimethyl)azanium;chloride Chemical compound [Cl-].CCCCCCCCCC[N+](C)(C)C HXWGXXDEYMNGCT-UHFFFAOYSA-M 0.000 claims description 2
- PLMFYJJFUUUCRZ-UHFFFAOYSA-M decyltrimethylammonium bromide Chemical compound [Br-].CCCCCCCCCC[N+](C)(C)C PLMFYJJFUUUCRZ-UHFFFAOYSA-M 0.000 claims description 2
- TYIXMATWDRGMPF-UHFFFAOYSA-N dibismuth;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Bi+3].[Bi+3] TYIXMATWDRGMPF-UHFFFAOYSA-N 0.000 claims description 2
- DDXLVDQZPFLQMZ-UHFFFAOYSA-M dodecyl(trimethyl)azanium;chloride Chemical compound [Cl-].CCCCCCCCCCCC[N+](C)(C)C DDXLVDQZPFLQMZ-UHFFFAOYSA-M 0.000 claims description 2
- XJWSAJYUBXQQDR-UHFFFAOYSA-M dodecyltrimethylammonium bromide Chemical compound [Br-].CCCCCCCCCCCC[N+](C)(C)C XJWSAJYUBXQQDR-UHFFFAOYSA-M 0.000 claims description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 2
- 125000003709 fluoroalkyl group Chemical group 0.000 claims description 2
- 125000001207 fluorophenyl group Chemical group 0.000 claims description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 2
- 229910052737 gold Inorganic materials 0.000 claims description 2
- 239000010931 gold Substances 0.000 claims description 2
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 2
- 229910052741 iridium Inorganic materials 0.000 claims description 2
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- 230000001678 irradiating effect Effects 0.000 claims description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 2
- 229910052746 lanthanum Inorganic materials 0.000 claims description 2
- 229910052749 magnesium Inorganic materials 0.000 claims description 2
- 239000011777 magnesium Substances 0.000 claims description 2
- 239000000395 magnesium oxide Substances 0.000 claims description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 2
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 2
- 229910001510 metal chloride Inorganic materials 0.000 claims description 2
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 2
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 2
- 125000001624 naphthyl group Chemical group 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- 229910000484 niobium oxide Inorganic materials 0.000 claims description 2
- URLJKFSTXLNXLG-UHFFFAOYSA-N niobium(5+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Nb+5].[Nb+5] URLJKFSTXLNXLG-UHFFFAOYSA-N 0.000 claims description 2
- 125000004365 octenyl group Chemical group C(=CCCCCCC)* 0.000 claims description 2
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- XCOHAFVJQZPUKF-UHFFFAOYSA-M octyltrimethylammonium bromide Chemical compound [Br-].CCCCCCCC[N+](C)(C)C XCOHAFVJQZPUKF-UHFFFAOYSA-M 0.000 claims description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 2
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 claims description 2
- BPUBBGLMJRNUCC-UHFFFAOYSA-N oxygen(2-);tantalum(5+) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Ta+5].[Ta+5] BPUBBGLMJRNUCC-UHFFFAOYSA-N 0.000 claims description 2
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 2
- 229910052763 palladium Inorganic materials 0.000 claims description 2
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 claims description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 2
- 229920002401 polyacrylamide Polymers 0.000 claims description 2
- 239000004584 polyacrylic acid Substances 0.000 claims description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 2
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 2
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 2
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 2
- 150000003242 quaternary ammonium salts Chemical group 0.000 claims description 2
- 229910052703 rhodium Inorganic materials 0.000 claims description 2
- 239000010948 rhodium Substances 0.000 claims description 2
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims description 2
- 229910052707 ruthenium Inorganic materials 0.000 claims description 2
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 2
- 229910052814 silicon oxide Inorganic materials 0.000 claims description 2
- 229910052709 silver Inorganic materials 0.000 claims description 2
- 239000004332 silver Substances 0.000 claims description 2
- VEALVRVVWBQVSL-UHFFFAOYSA-N strontium titanate Chemical compound [Sr+2].[O-][Ti]([O-])=O VEALVRVVWBQVSL-UHFFFAOYSA-N 0.000 claims description 2
- 239000005720 sucrose Substances 0.000 claims description 2
- 229910001936 tantalum oxide Inorganic materials 0.000 claims description 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 2
- SZEMGTQCPRNXEG-UHFFFAOYSA-M trimethyl(octadecyl)azanium;bromide Chemical compound [Br-].CCCCCCCCCCCCCCCCCC[N+](C)(C)C SZEMGTQCPRNXEG-UHFFFAOYSA-M 0.000 claims description 2
- AQZSPJRLCJSOED-UHFFFAOYSA-M trimethyl(octyl)azanium;chloride Chemical compound [Cl-].CCCCCCCC[N+](C)(C)C AQZSPJRLCJSOED-UHFFFAOYSA-M 0.000 claims description 2
- CEYYIKYYFSTQRU-UHFFFAOYSA-M trimethyl(tetradecyl)azanium;chloride Chemical compound [Cl-].CCCCCCCCCCCCCC[N+](C)(C)C CEYYIKYYFSTQRU-UHFFFAOYSA-M 0.000 claims description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 2
- 239000011787 zinc oxide Substances 0.000 claims description 2
- 229910052726 zirconium Inorganic materials 0.000 claims description 2
- 229910001928 zirconium oxide Inorganic materials 0.000 claims description 2
- 125000001424 substituent group Chemical group 0.000 claims 3
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 claims 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims 1
- 239000003973 paint Substances 0.000 claims 1
- 239000011230 binding agent Substances 0.000 abstract description 19
- 230000006866 deterioration Effects 0.000 abstract description 9
- 229910010413 TiO 2 Inorganic materials 0.000 description 73
- 239000000377 silicon dioxide Substances 0.000 description 26
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 description 24
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 19
- 238000006243 chemical reaction Methods 0.000 description 18
- 239000000126 substance Substances 0.000 description 17
- 238000006482 condensation reaction Methods 0.000 description 11
- 230000018044 dehydration Effects 0.000 description 11
- 238000006297 dehydration reaction Methods 0.000 description 11
- 238000011156 evaluation Methods 0.000 description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 10
- 239000000356 contaminant Substances 0.000 description 10
- 230000002829 reductive effect Effects 0.000 description 10
- 238000006460 hydrolysis reaction Methods 0.000 description 9
- 230000015572 biosynthetic process Effects 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- 239000008199 coating composition Substances 0.000 description 7
- 239000007788 liquid Substances 0.000 description 7
- 239000000376 reactant Substances 0.000 description 7
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 6
- 239000000725 suspension Substances 0.000 description 6
- 125000003277 amino group Chemical group 0.000 description 5
- 238000004458 analytical method Methods 0.000 description 5
- 239000002131 composite material Substances 0.000 description 5
- 230000007423 decrease Effects 0.000 description 5
- 238000009826 distribution Methods 0.000 description 5
- 229910002808 Si–O–Si Inorganic materials 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 239000012298 atmosphere Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000010335 hydrothermal treatment Methods 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 230000004913 activation Effects 0.000 description 3
- 238000004220 aggregation Methods 0.000 description 3
- 230000002776 aggregation Effects 0.000 description 3
- 239000004568 cement Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 239000003431 cross linking reagent Substances 0.000 description 3
- 230000003247 decreasing effect Effects 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 229910052602 gypsum Inorganic materials 0.000 description 3
- 239000010440 gypsum Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 230000007062 hydrolysis Effects 0.000 description 3
- 125000001165 hydrophobic group Chemical group 0.000 description 3
- 235000019645 odor Nutrition 0.000 description 3
- 238000007146 photocatalysis Methods 0.000 description 3
- 238000004381 surface treatment Methods 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 2
- 229920000877 Melamine resin Polymers 0.000 description 2
- 229910004298 SiO 2 Inorganic materials 0.000 description 2
- 150000004075 acetic anhydrides Chemical class 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 230000003373 anti-fouling effect Effects 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 125000002091 cationic group Chemical group 0.000 description 2
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 description 2
- 239000007859 condensation product Substances 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 239000002270 dispersing agent Substances 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000010408 film Substances 0.000 description 2
- 239000012467 final product Substances 0.000 description 2
- 150000003840 hydrochlorides Chemical class 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 244000005700 microbiome Species 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000002429 nitrogen sorption measurement Methods 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 230000001376 precipitating effect Effects 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000012495 reaction gas Substances 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 239000010865 sewage Substances 0.000 description 2
- 238000007873 sieving Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- UQMOLLPKNHFRAC-UHFFFAOYSA-N tetrabutyl silicate Chemical compound CCCCO[Si](OCCCC)(OCCCC)OCCCC UQMOLLPKNHFRAC-UHFFFAOYSA-N 0.000 description 2
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 description 2
- 229920000428 triblock copolymer Polymers 0.000 description 2
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 1
- DLOSDQIBVXBWTB-UHFFFAOYSA-N 1-[dimethyl(propyl)silyl]oxyethanamine Chemical compound CCC[Si](C)(C)OC(C)N DLOSDQIBVXBWTB-UHFFFAOYSA-N 0.000 description 1
- WUPHOULIZUERAE-UHFFFAOYSA-N 3-(oxolan-2-yl)propanoic acid Chemical compound OC(=O)CCC1CCCO1 WUPHOULIZUERAE-UHFFFAOYSA-N 0.000 description 1
- HXLAEGYMDGUSBD-UHFFFAOYSA-N 3-[diethoxy(methyl)silyl]propan-1-amine Chemical compound CCO[Si](C)(OCC)CCCN HXLAEGYMDGUSBD-UHFFFAOYSA-N 0.000 description 1
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 241000233866 Fungi Species 0.000 description 1
- 239000004640 Melamine resin Substances 0.000 description 1
- 229910003849 O-Si Inorganic materials 0.000 description 1
- 229910003872 O—Si Inorganic materials 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical group [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 239000005083 Zinc sulfide Substances 0.000 description 1
- CUPCBVUMRUSXIU-UHFFFAOYSA-N [Fe].OOO Chemical compound [Fe].OOO CUPCBVUMRUSXIU-UHFFFAOYSA-N 0.000 description 1
- TVOWJLRJDPSHSH-UHFFFAOYSA-N acetyl acetate;cerium Chemical compound [Ce].CC(=O)OC(C)=O TVOWJLRJDPSHSH-UHFFFAOYSA-N 0.000 description 1
- NMUTVZGCFBKTRR-UHFFFAOYSA-N acetyl acetate;zirconium Chemical compound [Zr].CC(=O)OC(C)=O NMUTVZGCFBKTRR-UHFFFAOYSA-N 0.000 description 1
- 125000003668 acetyloxy group Chemical group [H]C([H])([H])C(=O)O[*] 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 229920000180 alkyd Polymers 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000002519 antifouling agent Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000002238 attenuated effect Effects 0.000 description 1
- 238000007611 bar coating method Methods 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 1
- 125000001246 bromo group Chemical group Br* 0.000 description 1
- 125000004106 butoxy group Chemical group [*]OC([H])([H])C([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 1
- 229910052980 cadmium sulfide Inorganic materials 0.000 description 1
- 150000001721 carbon Chemical class 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000003093 cationic surfactant Substances 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- VYLVYHXQOHJDJL-UHFFFAOYSA-K cerium trichloride Chemical compound Cl[Ce](Cl)Cl VYLVYHXQOHJDJL-UHFFFAOYSA-K 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 239000008119 colloidal silica Substances 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 125000004093 cyano group Chemical group *C#N 0.000 description 1
- 238000007872 degassing Methods 0.000 description 1
- 238000004332 deodorization Methods 0.000 description 1
- 238000003618 dip coating Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 231100000507 endocrine disrupting Toxicity 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 239000011796 hollow space material Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 229910021519 iron(III) oxide-hydroxide Inorganic materials 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical compound [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 description 1
- 230000000670 limiting effect Effects 0.000 description 1
- 229910001629 magnesium chloride Inorganic materials 0.000 description 1
- WXPNTKUIDRYHOP-UHFFFAOYSA-L magnesium;3-oxobutanoate Chemical compound [Mg+2].CC(=O)CC([O-])=O.CC(=O)CC([O-])=O WXPNTKUIDRYHOP-UHFFFAOYSA-L 0.000 description 1
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 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
- 150000002736 metal compounds Chemical class 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000002991 molded plastic Substances 0.000 description 1
- 238000010137 moulding (plastic) Methods 0.000 description 1
- INJVFBCDVXYHGQ-UHFFFAOYSA-N n'-(3-triethoxysilylpropyl)ethane-1,2-diamine Chemical compound CCO[Si](OCC)(OCC)CCCNCCN INJVFBCDVXYHGQ-UHFFFAOYSA-N 0.000 description 1
- MQWFLKHKWJMCEN-UHFFFAOYSA-N n'-[3-[dimethoxy(methyl)silyl]propyl]ethane-1,2-diamine Chemical compound CO[Si](C)(OC)CCCNCCN MQWFLKHKWJMCEN-UHFFFAOYSA-N 0.000 description 1
- SLYCYWCVSGPDFR-UHFFFAOYSA-N octadecyltrimethoxysilane Chemical compound CCCCCCCCCCCCCCCCCC[Si](OC)(OC)OC SLYCYWCVSGPDFR-UHFFFAOYSA-N 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 230000036961 partial effect Effects 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 235000019353 potassium silicate Nutrition 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 238000007763 reverse roll coating Methods 0.000 description 1
- 238000007761 roller coating Methods 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 229920002050 silicone resin Polymers 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 238000002336 sorption--desorption measurement Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 230000001954 sterilising effect Effects 0.000 description 1
- 238000004659 sterilization and disinfection Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 1
- 125000003396 thiol group Chemical group [H]S* 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- LSGOVYNHVSXFFJ-UHFFFAOYSA-N vanadate(3-) Chemical compound [O-][V]([O-])([O-])=O LSGOVYNHVSXFFJ-UHFFFAOYSA-N 0.000 description 1
- 239000002023 wood 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
- 229910052984 zinc sulfide Inorganic materials 0.000 description 1
- DRDVZXDWVBGGMH-UHFFFAOYSA-N zinc;sulfide Chemical compound [S-2].[Zn+2] DRDVZXDWVBGGMH-UHFFFAOYSA-N 0.000 description 1
- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical compound Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 0.000 description 1
Landscapes
- Catalysts (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Paints Or Removers (AREA)
- Paper (AREA)
- Exhaust Gas Treatment By Means Of Catalyst (AREA)
Abstract
Description
本発明は、例えば空気中の有害物質、臭い若しくは汚れ等の除去に有用な光触媒、及びその作製方法に関する。 The present invention relates to a photocatalyst useful for removing, for example, harmful substances, odors or dirt in the air, and a production method thereof.
光触媒は、そのバンドギャップ以上のエネルギーを持つ光が照射されると励起し、強い触媒活性を発現する。そのため、特に有機物やＮＯｘ等の一部無機物の酸化・分解が可能である。また、光触媒は、エネルギー源として、低コストで環境負荷の非常に小さい光を利用できることから、近年環境浄化や脱臭、防汚、殺菌等へ応用されている。さらに、光触媒が励起するとその表面が親水性になり水との接触角が低下することが見出され、この作用を利用して防曇、防汚等への応用も進められている。このような光触媒は、通常、基体表面上に担持させて用いられる。 A photocatalyst is excited when irradiated with light having energy greater than its band gap, and exhibits a strong catalytic activity. Therefore, it is possible to oxidize and decompose some inorganic substances such as organic substances and NOx. In addition, the photocatalyst can be used as an energy source at low cost and with a very low environmental load, and has recently been applied to environmental purification, deodorization, antifouling, sterilization, and the like. Furthermore, it has been found that when the photocatalyst is excited, its surface becomes hydrophilic and the contact angle with water decreases, and application to antifogging, antifouling and the like is being promoted utilizing this action. Such a photocatalyst is usually used while being supported on the surface of a substrate.
しかし、光触媒を基体表面に担持させる際、通常例えばバインダー等が用いられるが、当該バインダーは、光触媒に光が照射されると、分解され褐変してしまう。そのため、特許文献１においては、多孔体の骨格が形成される前に、多孔体の前駆物質である液体、ゾル、またはゲル状の合成媒体に、例えば酸化チタンなどの光触媒粒子を混合分散させ、その後多孔体の骨格を形成させることにより、多孔体と光触媒粒子とが複合化した複合体を作製することが提案されている（特許文献１）。すなわち、多孔体の前駆物質と光触媒粒子とを含む溶液を用い、上記前駆物質を多孔体に変化させることにより、多孔体と光触媒粒子との複合体を作製する。このようにして作製された複合体では、多孔体により光触媒粒子が被覆され、光触媒粒子とバインダーとが直接接触しないため、バインダーの劣化の防止が期待される。
しかしながら、上記方法により作製された複合体（特許文献１）では、光触媒粒子を被覆したものが多孔性のものであるため、光触媒の活性サイトは全ては減殺されていないものの、光触媒の表面が直接被覆されているため、光触媒の活性サイトが著しく減少し、その光触媒機能が低下してしまうという問題があった。 However, in the composite prepared by the above method (Patent Document 1), the photocatalyst particle-coated one is porous, so that the active sites of the photocatalyst are not all attenuated, but the surface of the photocatalyst is directly Since it is coated, there is a problem that the active sites of the photocatalyst are remarkably reduced and the photocatalytic function is lowered.
したがって、本発明は、叙上に鑑みなされたものであり、その目的とするところは、バインダーの劣化を防止しつつ、光触媒機能の低下を抑制できる信頼性の高い光触媒及びその作製方法を提供することにある。 Therefore, the present invention has been made in view of the above, and an object of the present invention is to provide a highly reliable photocatalyst capable of suppressing deterioration of the photocatalytic function while preventing deterioration of the binder and a method for producing the same. There is.
本発明者らは、上記課題に鑑み鋭意研究を行った結果、光触媒粒子を含むコア部表面上に炭素含有層を形成し当該炭素含有層上に多孔質シェル層を形成した後炭素含有層を除去して、コア部と多孔質シェル層との間に中空層を介在させることにより、光触媒の活性サイトが殆ど減少せず、光触媒能が低下しないことを見出し、本発明を完成するに至った。 As a result of intensive studies in view of the above problems, the present inventors formed a carbon-containing layer on the surface of the core part including the photocatalyst particles, and then formed a porous shell layer on the carbon-containing layer. By removing and interposing a hollow layer between the core part and the porous shell layer, it was found that the active sites of the photocatalyst were hardly reduced and the photocatalytic ability was not lowered, and the present invention was completed. .
従って、本発明は、光触媒粒子を含むコア部と前記コア部から離間して当該コア部を覆う多孔質シェル層とを含む光触媒を作製する方法であって、１．前記コア部の表面の少なくとも一部に直接炭素含有層を形成する第一工程と、２．前記炭素含有層が形成されたコア部を懸濁させた溶媒に細孔形成剤を混合して、前記炭素含有層を細孔形成剤で被覆するとともに、当該溶媒中に細孔形成剤を分散させる第二工程と、３．前記溶媒中に多孔質シェル層の前駆物質を混合して、前記の炭素含有層表面を被覆する細孔形成剤の層上に、前記溶媒中に分散された細孔形成剤を含んでなる多孔質シェル層となる層を形成する第三工程と、４．前記コア部と前記多孔質シェル層となる層との間にある前記炭素含有層及び前記細孔形成剤並びに前記多孔質シェル層となる層の壁内に含まれる細孔形成剤を除去する第四工程と、を含むことを特徴とする光触媒の作製方法にある。 Accordingly, the present invention is a method for producing a photocatalyst comprising a core part containing photocatalyst particles and a porous shell layer that is spaced apart from the core part and covers the core part. 1. a first step of directly forming a carbon-containing layer on at least a part of the surface of the core part; A pore-forming agent is mixed in a solvent in which the core portion on which the carbon-containing layer is formed is suspended, and the carbon-containing layer is coated with the pore-forming agent, and the pore-forming agent is dispersed in the solvent. 2. a second step to be performed; A porous material comprising a pore-forming agent dispersed in the solvent on a layer of a pore-forming agent mixed with the precursor of the porous shell layer in the solvent and covering the surface of the carbon-containing layer. 3. a third step of forming a layer to become a porous shell layer; Removing the carbon-containing layer and the pore-forming agent between the core portion and the layer to be the porous shell layer, and the pore-forming agent contained in the walls of the layer to be the porous shell layer; And a four-step process for producing a photocatalyst.
また、本発明は、光触媒粒子を含むコア部と、前記コア部から離間して前記コア部を覆う多孔質シェル層と、を含み、前記コア部と前記多孔質シェル層との間には中空層が設けられてなる光触媒であって、窒素吸着法によって測定される、０．４〜５０ｎｍの範囲の細孔径の、単位重量当たりの細孔容積が０．１ｃｍ３／ｇ以上である光触媒にある。 The present invention also includes a core part including photocatalyst particles and a porous shell layer that covers the core part away from the core part, and a hollow space is formed between the core part and the porous shell layer. A photocatalyst provided with a layer, wherein the photocatalyst has a pore diameter in the range of 0.4 to 50 nm and a pore volume per unit weight of 0.1 cm 3 / g or more as measured by a nitrogen adsorption method. is there.
本発明によれば、コア部と多孔質シェル層との間にある炭素含有層を除去するため、コア部と多孔質シェル層との間に中空層が設けられることとなる。それにより、当該方法により作製される光触媒では、コア部と多孔質シェル層との間に中空層が介在するため、光触媒粒子の活性サイトが殆ど減少せず、光触媒機能が低下しない。 According to the present invention, a hollow layer is provided between the core portion and the porous shell layer in order to remove the carbon-containing layer between the core portion and the porous shell layer. Thereby, in the photocatalyst produced by the method, since the hollow layer is interposed between the core portion and the porous shell layer, the active sites of the photocatalyst particles are hardly reduced and the photocatalytic function is not lowered.
したがって、本発明によれば、バインダーの劣化を防止しつつ、光触媒機能の低下を抑制できる信頼性の高い光触媒及びその作製方法を提供することができる。 Therefore, according to the present invention, it is possible to provide a highly reliable photocatalyst capable of suppressing deterioration of the photocatalytic function while preventing deterioration of the binder and a method for producing the photocatalyst.
以下、図面を参照しながら、本発明に係る実施の形態の光触媒に関して説明する。しかしながら、以下に示す実施の形態は例示するものであって、これらに限定するものではない。また、本明細書において、同一部材については全図面を通して同一の参照番号により示している。また、本出願において、光触媒とは、光触媒粒子を含むコア部と多孔質シェル層とからなる一又は複数の複合体を、光触媒粒子とは、コア部に含まれるものであって、実際に汚染物質等の反応物質に光触媒作用を及ぼすものを意味する。 Hereinafter, a photocatalyst according to an embodiment of the present invention will be described with reference to the drawings. However, the embodiments described below are illustrative and not limiting. In the present specification, the same members are denoted by the same reference numerals throughout the drawings. Further, in the present application, the photocatalyst is one or more composites composed of a core part containing photocatalyst particles and a porous shell layer, and the photocatalyst particle is contained in the core part, and is actually contaminated. It means a substance that has a photocatalytic action on a reactive substance such as a substance.
（実施の形態１） (Embodiment 1)
以下に、本発明に係る光触媒の作製方法及び光触媒に関して、各構成要素毎に具体的に説明する。 Hereinafter, the photocatalyst preparation method and the photocatalyst according to the present invention will be specifically described for each component.
〈光触媒の作製方法〉
最初に、図３ａ〜図３ｅを参照しながら、本発明の好ましい実施の形態に係る光触媒の作製方法について説明する。本発明の好ましい実施形態に係る光触媒の作製方法は、１．コア部に含まれる光触媒粒子を準備する工程（光触媒粒子の準備工程）と、２．コア部の表面の少なくとも一部に直接炭素含有層を形成する工程（炭素含有層の形成工程）と、３．炭素含有層が形成されたコア部を懸濁させた溶媒に細孔形成剤を混合して、前記炭素含有層を細孔形成剤で被覆するとともに、当該溶媒中に細孔形成剤を分散させる工程（細孔形成剤の混合工程）と、４．溶媒中に多孔質シェル層の前駆物質を混合して、前記の炭素含有層表面を被覆する細孔形成剤の層上に、前記溶媒中に分散された細孔形成剤を含んでなる多孔質シェル層となる層を形成する工程（多孔質シェル層の形成工程）と、５．コア部と多孔質シェル層となる層との間にある前記炭素含有層及び前記細孔形成剤並びに前記多孔質シェル層となる層の壁内に含まれる細孔形成剤を除去する工程（炭素含有層及び細孔形成剤の除去工程）と、を含み、必要に応じて、６．光触媒を水素雰囲気下で熱処理し還元処理する工程（活性化処理工程）を含んでいてもよい。
<Method for producing photocatalyst>
First, a method for producing a photocatalyst according to a preferred embodiment of the present invention will be described with reference to FIGS. 3a to 3e. A method for producing a photocatalyst according to a preferred embodiment of the present invention is as follows. 1. a step of preparing photocatalyst particles contained in the core part (a step of preparing photocatalyst particles); 2. a step of directly forming a carbon-containing layer on at least a part of the surface of the core part (a step of forming a carbon-containing layer); A pore-forming agent is mixed with a solvent in which the core portion on which the carbon-containing layer is formed is suspended, and the carbon-containing layer is coated with the pore-forming agent, and the pore-forming agent is dispersed in the solvent. 3. process (mixing process of pore forming agent); A porous material comprising a pore-forming agent dispersed in the solvent on a layer of the pore-forming agent that covers the surface of the carbon-containing layer by mixing a precursor of the porous shell layer in a solvent 4. a step of forming a layer to be a shell layer (a step of forming a porous shell layer); A step of removing the carbon-containing layer and the pore-forming agent between the core portion and the layer to be the porous shell layer and the pore-forming agent contained in the walls of the layer to be the porous shell layer (carbon And a step of removing the content layer and the pore forming agent), and if necessary, 6. A step (activation treatment step) of subjecting the photocatalyst to heat treatment under a hydrogen atmosphere and reduction treatment may be included.
１）光触媒粒子の準備
まず、コア部１に含まれることとなる光触媒粒子を準備する（図３ａ）。当該光触媒粒子は、バルク状の光触媒粒子をナノスケールまで超微細化して作製してもよいし、析出沈殿法等により作製してもよい。光触媒粒子の大きさは、特に限定されるものではないが、好ましくは１ｎｍ〜２０μｍ、より好ましくは１ｎｍ〜１０００ｎｍ、さらに好ましくは１ｎｍ〜５００ｎｍ、さらに好ましくは１ｎｍ〜２５０ｎｍ、さらに好ましくは１ｎｍ〜１００ｎｍである。上記のように微細な光触媒粒子であれば、より高い光触媒機能が得られるため好ましい。
1) Preparation of photocatalyst particles First, photocatalyst particles to be included in the core portion 1 are prepared (FIG. 3a). The photocatalyst particles may be prepared by ultra-fine bulk photocatalyst particles to nanoscale, or may be prepared by a precipitation method or the like. The size of the photocatalyst particles is not particularly limited, but is preferably 1 nm to 20 μm, more preferably 1 nm to 1000 nm, further preferably 1 nm to 500 nm, still more preferably 1 nm to 250 nm, still more preferably 1 nm to 100 nm. is there. The fine photocatalyst particles as described above are preferable because a higher photocatalytic function can be obtained.
また、光触媒粒子をコア部の一部に含ませてもよいし、光触媒粒子自体をコア部とする、即ちコア部全体が光触媒粒子からなるようにしてもよい。 Further, the photocatalyst particles may be included in a part of the core part, or the photocatalyst particles themselves may be used as the core part, that is, the entire core part may be formed of the photocatalyst particles.
２）炭素含有層の形成
続いて、図３ｂに示すように、コア部１を構成することとなる光触媒粒子を、炭素含有層の前駆物質を含む水溶液に懸濁させ、これを上記溶液中で水熱処理し、コア部１の表面の一部、好ましくはその全部を炭素含有層２'で被覆する。当該水熱処理は、１５０〜２００℃で行うことが好ましく、更に好ましくは、１６０〜１８０℃である。このような範囲の温度で水熱処理を行うことにより、均一な炭素含有層が得られる。
また、好ましい水熱処理時間は、０．５〜６時間、より好ましくは１〜４時間である。ここで、炭素含有層形成に好適な前駆物質として、例えばグルコース、スクロース、フェノール、ピロール、及びフルフリルアルコールが挙げられる。
2) Formation of carbon-containing layer Subsequently, as shown in FIG. 3b, the photocatalyst particles constituting the core part 1 are suspended in an aqueous solution containing the precursor of the carbon-containing layer, and this is suspended in the above solution. A part of the surface of the core part 1, preferably the whole, is covered with the carbon-containing layer 2 ′ by hydrothermal treatment. The hydrothermal treatment is preferably performed at 150 to 200 ° C, more preferably 160 to 180 ° C. By performing hydrothermal treatment at a temperature in such a range, a uniform carbon-containing layer can be obtained.
Moreover, the preferable hydrothermal treatment time is 0.5 to 6 hours, more preferably 1 to 4 hours. Here, examples of suitable precursors for forming the carbon-containing layer include glucose, sucrose, phenol, pyrrole, and furfuryl alcohol.
３）細孔形成剤の混合工程
続いて、上述のようにして形成された炭素含有層被覆光触媒粒子と細孔形成剤とを溶媒に混合し懸濁させて、懸濁溶液を調製する。これにより、図３ｃに示すように、炭素含有層２’の表面が細孔形成剤で被覆され炭素含有層２’上に細孔形成剤の層３が形成されるとともに、当該溶媒中に細孔形成剤からなるミセル６を生成される。ここで、細孔形成剤は、細孔を形成するための鋳型となるだけでなく、多孔質シェル層の前駆物質を炭素含有層２’へ引きつける機能を有することが必要である。このような細孔形成剤として、例えば、界面活性剤、特にカチオン性の界面活性剤が好適に用いられる。ここで、上記界面活性剤としては、
また、炭素含有層被覆光触媒粒子と細孔形成剤とが混合される溶媒としては、水が用いられる。 Water is used as a solvent in which the carbon-containing layer-coated photocatalyst particles and the pore-forming agent are mixed.
４）多孔質シェル層の形成工程
続いて、炭素含有層２'により被覆された光触媒粒子を含む上記懸濁溶液に、多孔質シェル層の前駆物質、例えばテトラエトキシシラン（ＴＥＯＳ）を混合する。これにより、図３ｄに示すように、多孔質シェル層４が、細孔形成剤の層３を起点として成長し、細孔形成剤の層３の上に形成される。ここで、多孔質シェル層４の前駆物質として、例えばＴＥＯＳを用いる場合、多孔質シェル層４は、ＴＥＯＳを加水分解・脱水縮合させることにより形成される。具体的には、下記式Ｉに従って、ＴＥＯＳ（Ｓｉ（ＯＣ２Ｈ５）４）を加水分解し、Ｓｉ（ＯＨ）４を生成する（式Ｉ）。このＳｉ（ＯＨ）４は、上記細孔形成剤の層３に引きつけられて細孔形成剤の層３を被覆する一方、このＳｉ（ＯＨ）４は式IIに従ってその水酸基同士が脱水縮合反応することにより結合する。これにより、架橋構造が成長しシリカ層が形成される。
4) Step of forming porous shell layer Subsequently, a precursor of the porous shell layer, for example, tetraethoxysilane (TEOS) is mixed with the suspension solution containing the photocatalyst particles covered with the carbon-containing layer 2 ′. Thereby, as shown in FIG. 3 d, the porous shell layer 4 grows from the pore-forming agent layer 3 as a starting point, and is formed on the pore-forming agent layer 3. Here, when TEOS, for example, is used as the precursor of the porous shell layer 4, the porous shell layer 4 is formed by hydrolyzing and dehydrating and condensing TEOS. Specifically, according to the following formula I, TEOS (Si (OC 2 H 5 ) 4 ) is hydrolyzed to produce Si (OH) 4 (formula I). The Si (OH) 4 is attracted to the pore-forming agent layer 3 to cover the pore-forming agent layer 3, while the Si (OH) 4 undergoes dehydration condensation reaction between the hydroxyl groups according to the formula II. To join. Thereby, a crosslinked structure grows and a silica layer is formed.
以下に、ＴＥＯＳの加水分解反応及び脱水縮合反応の一例を示す。
Ｉ．加水分解反応
Ｓｉ(ＯＣ２Ｈ５)４＋４Ｈ２Ｏ→Ｓｉ(ＯＨ)４＋４Ｃ２Ｈ５ＯＨ
II．脱水縮合反応
Ｓｉ(ＯＨ)４＋Ｓｉ(ＯＨ)４→(ＯＨ)３Ｓｉ−Ｏ−Ｓｉ(ＯＨ)３＋Ｈ２Ｏ
An example of TEOS hydrolysis reaction and dehydration condensation reaction is shown below.
I. Hydrolysis reaction Si (OC 2 H 5 ) 4 + 4H 2 O → Si (OH) 4 + 4C 2 H 5 OH
II. Dehydration condensation reaction Si (OH) 4 + Si (OH) 4 → (OH) 3 Si—O—Si (OH) 3 + H 2 O
このように、脱水縮合反応により結合してシリカの架橋構造が形成されるに際し、多孔質シェル層となる層は、界面活性剤からなるミセル６を取り込みながら成長する。そのため、多孔質シェル層となる層内には、ミセル６が分散することとなり、このミセル６を消失させれば、これが細孔７となる。したがって、界面活性剤の疎水基の鎖長を調整することにより、最終製品に係る光触媒の多孔質シェル層４の細孔径を調整することができる。また、細孔形成剤の濃度を調整することにより多孔質シェル層４の気孔率を調整することもできる。 As described above, when the silica cross-linked structure is formed by the dehydration condensation reaction, the layer that becomes the porous shell layer grows while taking in the micelles 6 made of the surfactant. Therefore, the micelles 6 are dispersed in the layer that becomes the porous shell layer. If these micelles 6 disappear, these become the pores 7. Therefore, the pore size of the porous shell layer 4 of the photocatalyst according to the final product can be adjusted by adjusting the chain length of the hydrophobic group of the surfactant. Further, the porosity of the porous shell layer 4 can be adjusted by adjusting the concentration of the pore forming agent.
多孔質シェル層の前駆物質としては、ＴＥＯＳの他、テトラメトキシシラン（ＴＭＯＳ）、テトラブトキシシラン（ＴＢＯＳ）等を用いることができる。 As a precursor for the porous shell layer, TEmethoxy, tetramethoxysilane (TMOS), tetrabutoxysilane (TBOS), or the like can be used.
また、本発明に係る光触媒の作製方法において、細孔形成剤の混合工程及び多孔質シェル層の形成工程は、塩基性下で行われることが好ましい。これは、塩基性において上記脱水縮合反応が適度な速さで進み、その結果良好な多孔質シェル層が得られるからである。
また、別の形態では、２）炭素含有層の形成工程で作製された炭素含有層被覆光触媒粒子と細孔形成剤と多孔質シェル層の前駆物質とを同時に溶媒に混合して、３）細孔形成剤の混合工程と４）多孔質シェル層の形成工程を同時に行ってもよい。これらの工程を同時に行うことにより、光触媒の製造工程を簡略化することができるため好ましい。
In the method for producing a photocatalyst according to the present invention, the step of mixing the pore forming agent and the step of forming the porous shell layer are preferably performed under basicity. This is because the above dehydration condensation reaction proceeds at an appropriate speed in basicity, and as a result, a good porous shell layer can be obtained.
In another embodiment, 2) the carbon-containing layer-coated photocatalyst particles prepared in the carbon-containing layer forming step, the pore-forming agent, and the precursor of the porous shell layer are mixed in a solvent at the same time, and 3) The pore forming agent mixing step and 4) the porous shell layer forming step may be performed simultaneously. It is preferable to perform these steps at the same time because the photocatalyst production process can be simplified.
５）炭素含有層及び細孔形成剤の除去工程
続いて、図３ｅに示すように、多孔質シェル層４が形成された光触媒を加熱することにより、多孔質シェル層４とコア部１との間に形成された炭素含有層２'及び細孔形成剤の層３並びに多孔質シェル層４となる層の壁内に含まれる細孔形成剤を除去する。ここで、除去された部分が中空層２となる。ここで、光触媒を加熱する際の加熱温度としては、４５０℃〜９００℃が好ましく、６００℃〜７００℃がさらに好ましい。
5) Step of removing carbon-containing layer and pore forming agent Subsequently, as shown in FIG. 3e, by heating the photocatalyst on which the porous shell layer 4 is formed, the porous shell layer 4 and the core portion 1 are separated. The pore-forming agent contained in the wall of the layer that becomes the carbon-containing layer 2 ′, the pore-forming agent layer 3 and the porous shell layer 4 formed therebetween is removed. Here, the removed portion becomes the hollow layer 2. Here, as heating temperature at the time of heating a photocatalyst, 450 to 900 degreeC is preferable, and 600 to 700 degreeC is more preferable.
６）活性化処理工程
その後、コア部１が金属を担持する光触媒粒子を含む場合は、金属化合物を担持した光触媒粒子を必要に応じて水素雰囲気下で熱処理を行うことで金属化合物を金属に還元することができる。
6) Activation treatment step After that, when the core part 1 contains photocatalyst particles carrying a metal, the metal compound is reduced to a metal by performing a heat treatment in a hydrogen atmosphere if necessary. can do.
〈光触媒〉
続いて、本発明に係る光触媒に関して詳細に説明する。本発明に係る光触媒は、上述の作製方法に限定されるものではなく、如何なる方法により作製することができる。
本発明の実施の形態に係る光触媒は、図１に示すように、光触媒粒子を含むコア部１と、コア部１を離間して覆う多孔質シェル層４と、を備え、コア部１と多孔質シェル層４との間に中空層２が介在する。さらに、コア部１と多孔質シェル層４と中空層２とから成る当該光触媒は、窒素吸着法によって測定される、０．４〜５０ｎｍの範囲の細孔径の細孔容積が０．１ｃｍ３／ｇ以上であることを特徴とする。
<photocatalyst>
Next, the photocatalyst according to the present invention will be described in detail. The photocatalyst according to the present invention is not limited to the above production method, and can be produced by any method.
As shown in FIG. 1, the photocatalyst according to the embodiment of the present invention includes a core portion 1 including photocatalytic particles and a porous shell layer 4 that covers the core portion 1 while being spaced apart. The hollow layer 2 is interposed between the porous shell layer 4. Furthermore, the photocatalyst composed of the core part 1, the porous shell layer 4 and the hollow layer 2 has a pore volume of 0.1 cm 3 / pore in a pore diameter in the range of 0.4 to 50 nm as measured by a nitrogen adsorption method. g or more.
一般に２ｎｍ以下の細孔径を有するものをミクロ孔、２〜５０ｎｍの範囲の細孔径を有するものをメソ孔、５０ｎｍ以上の細孔径を有するものをマクロ孔と称するが、本発明に係る光触媒は、ミクロ孔、メソ孔、マクロ孔全てを含んでいてもよい。本発明の光触媒において、特に、０．４〜５０ｎｍの範囲の細孔径を有する細孔（ミクロ孔およびメソ細孔）の細孔容積を０．１ｃｍ３／ｇ以上、より好ましくは０．５ｃｍ３／ｇ以上とする。細孔径、細孔容積を上記範囲とすることにより、汚染物質等の反応物の通過が阻害されない。
ここで、細孔容積の測定は、窒素吸着法によって行われる。窒素吸着法とは、多孔体を液体窒素温度に保ち、窒素分圧の関数として吸着量を測定することによって吸着等温線を得、吸着モデルに基づいて、その細孔構造を解析するものであり、約０．４ｎｍ〜１００ｎｍの範囲の細孔を測定することが可能である。
Generally, those having a pore diameter of 2 nm or less are called micropores, those having a pore diameter in the range of 2 to 50 nm are called mesopores, and those having a pore diameter of 50 nm or more are called macropores. All of micropores, mesopores, and macropores may be included. In the photocatalyst of the present invention, in particular, the pore volume of pores (micropores and mesopores) having a pore diameter in the range of 0.4 to 50 nm is 0.1 cm 3 / g or more, more preferably 0.5 cm 3. / G or more. By setting the pore diameter and pore volume within the above ranges, passage of reactants such as contaminants is not inhibited.
Here, the pore volume is measured by a nitrogen adsorption method. The nitrogen adsorption method is to maintain the porous body at the temperature of liquid nitrogen, measure the amount of adsorption as a function of nitrogen partial pressure, obtain the adsorption isotherm, and analyze the pore structure based on the adsorption model. It is possible to measure pores in the range of about 0.4 nm to 100 nm.
また、本発明に係る光触媒において、窒素吸着法によって測定される、０．４〜５０ｎｍの範囲の細孔径の細孔容積が、全細孔容積に対して、好ましくは５０％以上、より好ましくは８０％以上であることを特徴とする。このような範囲とすることにより、ホルムアルデヒド等のサイズの小さい分子（１ｎｍ以下）のほか、内分泌かく乱物質（〜２ｎｍ）、及び人体に有害な各種石油系炭化水素（５〜１０ｎｍ程度）等の比較的分子サイズの大きい物質等の分解が可能になる。すなわち、前記のように０．４〜５０ｎｍの細孔径の容積率が高いと、その細孔を通過する汚染物質等の反応物と通過しないものとが選別され、通過したものだけが光触媒粒子によって分解される。このため、特定の大きさを持つ、汚染物質等の反応物だけを分解できるという分子ふるい作用を持たせることができる。
また、本発明に係る光触媒において、ＢＥＴ比表面積は、５０ｍ２／ｇ以上が好ましく、１００ｍ２／ｇ以上がより好ましく、より一層好ましくは１５０〜７００ｍ２／ｇ、さらに好ましくは２００〜６００ｍ２／ｇである。ＢＥＴ比表面積をこのような範囲とすることにより、上記同様汚染物質等の反応物の通過が阻害されず、分解が効率よくすすむ。
In the photocatalyst according to the present invention, the pore volume having a pore diameter in the range of 0.4 to 50 nm, measured by a nitrogen adsorption method, is preferably 50% or more, more preferably, relative to the total pore volume. It is characterized by being 80% or more. In this range, small molecules such as formaldehyde (less than 1 nm), endocrine disrupting substances (up to 2 nm), and various petroleum hydrocarbons that are harmful to the human body (about 5 to 10 nm) are compared. It is possible to decompose substances with a large molecular size. That is, when the volume ratio of the pore diameter of 0.4 to 50 nm is high as described above, the reactants such as contaminants that pass through the pores and those that do not pass through are selected, and only those that have passed through the photocatalyst particles. Disassembled. For this reason, it is possible to provide a molecular sieving action that can decompose only reactants such as contaminants having a specific size.
Further, the photocatalyst according to the present invention, BET specific surface area is preferably at least 50m 2 / g, 100m 2 / g or more, and even more preferably 150~700m 2 / g, more preferably 200~600m 2 / g. By setting the BET specific surface area in such a range, the passage of reactants such as contaminants is not inhibited as in the case described above, and the decomposition proceeds efficiently.
当該光触媒において、多孔質シェル層４は多孔質組織となっているため、光触媒作用を受けるべき反応物質は、多孔質組織から多孔質シェル層４内に侵入し、コア部１に含まれる光触媒粒子に接触して光触媒作用を受ける。一方、光触媒を固定するための樹脂や高分子からなるバインダーは、そのサイズが大きく上記多孔質組織を通過し難いため、当該バインダーと光触媒粒子との接触が抑制され、バインダーの光触媒粒子による分解及びそれに伴う褐変が抑制される。 In the photocatalyst, since the porous shell layer 4 has a porous structure, the reactant to be subjected to the photocatalytic action enters the porous shell layer 4 from the porous structure and is included in the core part 1. Contacted with photocatalysis. On the other hand, since the binder made of a resin or polymer for fixing the photocatalyst is large in size and difficult to pass through the porous structure, the contact between the binder and the photocatalyst particles is suppressed, and the binder is decomposed by the photocatalyst particles. Browning accompanying it is suppressed.
このように、反応物質については多孔質シェル層を通過させるが、バインダーについては通過させないというように分子ふるい現象を発現させるためには、上述のように、例えば界面活性剤等の細孔形成剤を用いて多孔質シェル層の細孔径を適宜調整することが肝要である。細孔形成剤は、細孔を形成するための鋳型となるものであり、シェル層に取り込まれその後加熱処理によりシェル層から消失され、鋳型の役割を果たす。例えば、細孔形成剤として、界面活性剤を使用する場合、当該界面活性剤に含まれる疎水基の鎖長を大きくすれば、当該界面活性剤により形成されるミセル径は大きくなる。多孔質シェル層は、溶媒中に分散されている上記ミセルを取り込ながら成長するため、多孔質シェル層に含まれる細孔の径は、ミセルの径に略一致することとなる。したがって、界面活性剤に含まれる疎水基の鎖長を大きくすれば、多孔質シェル層の細孔径は大きくなり、当該鎖長を小さくすれば、多孔質シェル層の細孔径は小さくなる。よって、光触媒作用を受けるべき汚染物質のクラスターの大きさと、光触媒を固定するためのバインダーの分子の大きさとを考慮しながら、多孔質シェル層の細孔径を適切な範囲に調整すれば、バインダーの劣化を防止しつつ、光触媒機能を良好に発揮させることができる。 Thus, in order to express the molecular sieving phenomenon such that the reactant is allowed to pass through the porous shell layer but the binder is not allowed to pass through, as described above, for example, a pore forming agent such as a surfactant. It is important to appropriately adjust the pore diameter of the porous shell layer using The pore-forming agent serves as a template for forming pores, and is taken into the shell layer and then disappears from the shell layer by heat treatment, and serves as a template. For example, when a surfactant is used as the pore forming agent, if the chain length of the hydrophobic group contained in the surfactant is increased, the micelle diameter formed by the surfactant is increased. Since the porous shell layer grows while taking in the micelles dispersed in the solvent, the diameter of the pores contained in the porous shell layer substantially matches the diameter of the micelle. Therefore, if the chain length of the hydrophobic group contained in the surfactant is increased, the pore diameter of the porous shell layer is increased, and if the chain length is decreased, the pore diameter of the porous shell layer is decreased. Therefore, if the pore size of the porous shell layer is adjusted to an appropriate range in consideration of the size of the contaminant cluster to be subjected to photocatalysis and the size of the binder molecule for fixing the photocatalyst, The photocatalytic function can be satisfactorily exhibited while preventing deterioration.
また、細孔形成剤は、多孔質シェル層の細孔形成に寄与する以外にも、炭素含有層と多孔質シェル層の前駆物質との親和性を高める機能も有する。これは、細孔形成剤が、炭素含有層の表面上に層をなし、当該層の最外表面が当該前駆物質を引きつけやすい状態になっているためであると考えられる。ここで、多孔質シェル層の細孔形成に寄与する細孔形成剤と、炭素含有層と多孔質シェル層の前駆物質との親和性を高めるのに寄与するものとは、異なるものであってもよい。しかしながら、製造工程簡略化の観点からするとそれらは同一のものであることが好ましい。 In addition to contributing to pore formation of the porous shell layer, the pore forming agent also has a function of increasing the affinity between the carbon-containing layer and the precursor of the porous shell layer. This is considered to be because the pore forming agent forms a layer on the surface of the carbon-containing layer, and the outermost surface of the layer is in a state in which the precursor is easily attracted. Here, the pore-forming agent that contributes to the pore formation of the porous shell layer and the one that contributes to increase the affinity between the carbon-containing layer and the precursor of the porous shell layer are different. Also good. However, from the viewpoint of simplifying the manufacturing process, they are preferably the same.
また、光触媒粒子の直径をナノオーダーまで近づけると、高い光触媒活性を示すようになるが、表面エネルギーが非常に大きくなり分散不安定となるため、次第に光触媒粒子が凝集してしまう。そうなると光触媒粒子の表面積が減少することとなり、光触媒活性が著しく低下してしまう。しかしながら、本発明では、光触媒粒子を含むより少ない数のコア部が多孔質シェル層により被覆されているため、凝集が防止され、光触媒活性の低下を抑制することができる。 Further, when the diameter of the photocatalyst particles is brought close to the nano order, high photocatalytic activity is exhibited. However, since the surface energy becomes very large and dispersion becomes unstable, the photocatalyst particles gradually aggregate. If it becomes so, the surface area of a photocatalyst particle will reduce and photocatalytic activity will fall remarkably. However, in the present invention, since a smaller number of core parts including the photocatalyst particles are covered with the porous shell layer, aggregation is prevented and a decrease in photocatalytic activity can be suppressed.
また、本発明では、光触媒粒子を含むコア部１を多孔質体で直接被覆するのではなく、コア部１と多孔質シェル層４との間に中空層２を介在させてコア部１を多孔質体で被覆するため、コア部１に含まれる光触媒粒子の活性サイトは減少しない。そのため、光触媒活性の低下を抑制することができる。 In the present invention, the core portion 1 containing the photocatalyst particles is not directly covered with the porous body, but the core portion 1 is made porous by interposing the hollow layer 2 between the core portion 1 and the porous shell layer 4. Since it is coated with a material, the active sites of the photocatalyst particles contained in the core portion 1 are not reduced. Therefore, it is possible to suppress a decrease in photocatalytic activity.
また、光触媒の直径は、５０ｎｍ〜２５μｍであることが好ましい。光触媒の回収のし易さ等のためである。 The diameter of the photocatalyst is preferably 50 nm to 25 μm. This is because the photocatalyst can be easily recovered.
〈光触媒粒子〉
光触媒粒子は、主にコア部１に含まれ、汚染物質等を光触媒作用により酸化分解する。この光触媒粒子は多孔質シェル層４に含まれていても良い。このような光触媒粒子として、光触媒作用を及ぼす物質であれば如何なるものであっても良いが、例示すれば、酸化チタン、チタン酸ストロンチウム、酸化亜鉛、酸化銅、酸化ビスマス、酸化タングステン、酸化鉄、酸化ニオブ、酸化タンタル、硫化カドミウム、硫化亜鉛、ビスマスバナジウム酸塩、アルカリ金属チタン酸塩、アルカリ金属ニオブ酸塩が挙げられ、これらのうち少なくとも１種を組み合わせてもよい。
<Photocatalyst particles>
The photocatalyst particles are mainly contained in the core portion 1 and oxidatively decompose contaminants and the like by photocatalytic action. The photocatalyst particles may be contained in the porous shell layer 4. As such a photocatalyst particle, any substance having a photocatalytic action may be used. For example, titanium oxide, strontium titanate, zinc oxide, copper oxide, bismuth oxide, tungsten oxide, iron oxide, Examples thereof include niobium oxide, tantalum oxide, cadmium sulfide, zinc sulfide, bismuth vanadate, alkali metal titanate, and alkali metal niobate, and at least one of them may be combined.
光触媒作用の観点から、酸化チタンを用いることが好ましい。ここで、光触媒粒子として酸化チタンを用いる場合、これは、アナターゼ型、ブルッカイト型、ルチル型等のうちいずれのタイプであってもよく、また、これらの混晶タイプのものであってもよい。しかし、微粒子が容易に得られることなどから、アナターゼ型を用いることがより好ましい。 From the viewpoint of photocatalysis, titanium oxide is preferably used. Here, when titanium oxide is used as the photocatalyst particles, this may be any type of anatase type, brookite type, rutile type, etc., or may be a mixed crystal type of these. However, it is more preferable to use the anatase type because fine particles can be easily obtained.
また、当該光触媒粒子に、白金、ロジウム、ルテニウム、パラジウム、金、銀、銅、ニッケル、鉄及びイリジウムからなる群から選択される少なくとも１種の金属を担持することが好ましい。これらの金属を光触媒粒子に担持させることにより、励起光照射により発生する電子と正孔との再結合を抑制し、光触媒活性の低下を防止することができる。これは、上記金属を担持させると、当該金属の集電効果によりこれが電子を引き寄せることができるからである。 Moreover, it is preferable that the photocatalyst particles carry at least one metal selected from the group consisting of platinum, rhodium, ruthenium, palladium, gold, silver, copper, nickel, iron, and iridium. By supporting these metals on the photocatalyst particles, recombination of electrons and holes generated by excitation light irradiation can be suppressed, and a decrease in photocatalytic activity can be prevented. This is because when the metal is supported, it can attract electrons due to the current collecting effect of the metal.
また、光触媒粒子は、可視光の照射により励起される可視光応答型光触媒粒子であることが好ましい。通常酸化チタンを励起しうる紫外光は、自然光中に数％しか含まれていない。そのため、酸化チタンの光触媒作用は効果的であるとは言えない。しかし、光触媒粒子を当該可視光応答型とすることにより、自然光を有効に利用して汚染物質を効果的に分解することができる。ここで、可視光応答型光触媒粒子は公知のものを用いることができるが、例えば、酸化チタン等の紫外光利用型光触媒粒子に硫黄（Ｓ）、窒素（Ｎ）、炭素（Ｃ）等の異種元素をドープしたもの、紫外光利用型光触媒粒子に異種の金属イオンを固溶させたもの、ハロゲン化白金化合物やオキシ水酸化鉄等を光触媒粒子の表面に担持させたもの、あるいは酸化チタン粒子と酸化鉄、酸化タングステンなど可視光領域で光触媒活性が発現する化合物とを複合したもの、酸化チタンのチタンと酸素の組成を変えたものなどを好適に用いることができる。 The photocatalyst particles are preferably visible light responsive photocatalyst particles that are excited by irradiation with visible light. Usually, only a few percent of the ultraviolet light that can excite titanium oxide is contained in natural light. Therefore, it cannot be said that the photocatalytic action of titanium oxide is effective. However, by using the photocatalyst particles as the visible light responsive type, pollutants can be effectively decomposed by effectively using natural light. Here, the visible light responsive photocatalyst particles may be known ones. For example, the ultraviolet light utilizing photocatalyst particles such as titanium oxide may be different from sulfur (S), nitrogen (N), carbon (C) and the like. Elements doped with ultraviolet light, photocatalyst particles utilizing ultraviolet light with different metal ions dissolved, platinum halide compounds or iron oxyhydroxide supported on the surface of photocatalyst particles, or titanium oxide particles A compound in which a compound that exhibits photocatalytic activity in the visible light region, such as iron oxide or tungsten oxide, or a compound in which the composition of titanium and oxygen of titanium oxide is changed can be suitably used.
〈コア部〉
コア部１は、光触媒粒子を含んでなり、中空層２を介して多孔質シェル層４により被覆されている。ここで、コア部１は、多孔質シェル層４内に複数存在しても良い。しかしながら、複数コア部１が含まれる場合は、コア部１がナノオーダーの径を有する場合、凝集して光触媒活性が低下してしまう。そのため、多孔質シェル層４内に含まれるコア部１はできるだけ少ないことが好ましい。また、コア部１の形状は、製造上の観点から、略球形であることが好ましい。しかし、光触媒機能を良好に発揮しうる限り、如何なる形状であっても良い。コア部１が略球形である場合、その直径は１ｎｍ〜２０μｍでの範囲にあることが好ましく、１ｎｍ〜１μｍの範囲にあることがより好ましく、１ｎｍ〜５００ｎｍの範囲にあることがより好ましく、１ｎｍ〜２５０ｎｍの範囲がより好ましく、１ｎｍ〜１００ｎｍの範囲にあることがさらに好ましい。コア部１の直径を上記の範囲に設定すれば、高い光触媒活性が得られる。
<Core part>
The core portion 1 includes photocatalyst particles and is covered with a porous shell layer 4 via a hollow layer 2. Here, a plurality of core portions 1 may exist in the porous shell layer 4. However, when the multiple core portions 1 are included, if the core portion 1 has a nano-order diameter, the photocatalytic activity is reduced due to aggregation. Therefore, it is preferable that the core part 1 contained in the porous shell layer 4 is as few as possible. Moreover, it is preferable that the shape of the core part 1 is a substantially spherical shape from a viewpoint on manufacture. However, any shape is possible as long as the photocatalytic function can be satisfactorily exhibited. When the core part 1 is substantially spherical, the diameter thereof is preferably in the range of 1 nm to 20 μm, more preferably in the range of 1 nm to 1 μm, more preferably in the range of 1 nm to 500 nm. The range of ˜250 nm is more preferable, and the range of 1 nm to 100 nm is more preferable. When the diameter of the core part 1 is set in the above range, high photocatalytic activity can be obtained.
また、光触媒粒子はコア部１の少なくとも一部に含まれていればよいが、製造上の観点からコア部全体が、光触媒粒子から構成されていることが好ましい。このようにコア部全体が光触媒粒子から構成されていると、光触媒粒子の表面がより多く露出されることになり、光触媒の活性サイトを有効に利用することができる。 Moreover, although the photocatalyst particle should just be contained in at least one part of the core part 1, it is preferable that the whole core part is comprised from the photocatalyst particle from a viewpoint on manufacture. When the entire core part is composed of the photocatalyst particles in this way, the surface of the photocatalyst particles is more exposed, and the active sites of the photocatalyst can be used effectively.
また、コア部１は中空状であっても良い。さらに、コア部１は、少なくとも一部に多孔質組織を有し、その多孔質組織の微細孔に微小な光触媒粒子が分散された形態であっても良い。コア部１が、多孔質組織を含んでいると、光が照射されていない間に汚染物質等をこの多孔質組織に吸着し、その後光が照射される時に、多孔質組織に吸着された汚染物質を分解することができる。 The core portion 1 may be hollow. Furthermore, the core part 1 may have a form in which at least a part has a porous structure and fine photocatalyst particles are dispersed in the micropores of the porous structure. When the core portion 1 includes a porous tissue, the contaminants and the like are adsorbed to the porous tissue while the light is not irradiated, and then the contamination adsorbed to the porous tissue when the light is irradiated. The substance can be decomposed.
〈多孔質シェル層〉
多孔質シェル層４は、光触媒粒子を含むコア部１を中空層を介して覆っており、例えば、光触媒を固定するためのバインダーと光触媒粒子を含むコア部との接触を抑制するためのものである。また、このように多孔質シェル層４で覆うことにより、光触媒粒子の凝集を防止することもできる。
<Porous shell layer>
The porous shell layer 4 covers the core portion 1 containing the photocatalyst particles via a hollow layer, and is for suppressing the contact between the binder for fixing the photocatalyst and the core portion containing the photocatalyst particles, for example. is there. Further, by covering with the porous shell layer 4 in this way, aggregation of the photocatalyst particles can be prevented.
多孔質シェル層４は、図１に示すような中空状であって、多孔質シェル層４の少なくとも一部に多孔質組織を含む。多孔質シェル層４の形状は球状に限定されず、如何なる形状であっても良い。しかし、製造の観点からすると、当該形状はコア部１の形状と同様の形状であることが好ましい。 The porous shell layer 4 has a hollow shape as shown in FIG. 1 and includes a porous structure in at least a part of the porous shell layer 4. The shape of the porous shell layer 4 is not limited to a spherical shape, and may be any shape. However, from the viewpoint of manufacturing, the shape is preferably the same shape as the core portion 1.
また、多孔質シェル層４の直径は、５０ｎｍ〜５μｍであることが好ましい。光触媒の回収のし易さ等のためである。 The diameter of the porous shell layer 4 is preferably 50 nm to 5 μm. This is because the photocatalyst can be easily recovered.
さらに、多孔質シェル層４の気孔率及び微細孔の径は、多孔質シェル層４外から汚染物質、臭い、汚水、微生物等を通過させ、かつ、コア部１が流出しないような大きさであれば如何なる大きさであってもよい。多孔質シェル層４の気孔率としては、１０ｖｏｌ％〜９０ｖｏｌ％であることが好ましく、２０ｖｏｌ％〜８０ｖｏｌ％であることがより好ましく、３０ｖｏｌ％〜７０ｖｏｌ％であることがさらに好ましい。また、多孔質シェル層４の多孔質構造の微細孔径としては、０．１ｎｍ〜１００ｎｍであることが好ましく、０．４〜５０ｎｍであることがより好ましく、１ｎｍ〜１０ｎｍであることがさらに好ましい。 Furthermore, the porosity of the porous shell layer 4 and the diameter of the micropores are such that contaminants, odors, sewage, microorganisms, and the like are allowed to pass from the outside of the porous shell layer 4 and the core portion 1 does not flow out. Any size is acceptable. The porosity of the porous shell layer 4 is preferably 10 vol% to 90 vol%, more preferably 20 vol% to 80 vol%, and even more preferably 30 vol% to 70 vol%. Moreover, as a micropore diameter of the porous structure of the porous shell layer 4, it is preferable that it is 0.1-100 nm, It is more preferable that it is 0.4-50 nm, It is further more preferable that it is 1-10 nm.
また、特に好ましい多孔質シェル層４は、０．４〜５０ｎｍの範囲の細孔径を有する細孔（ミクロ孔及びメソ細孔）の細孔容積が０．１ｃｍ３／ｇ以上であり、より好ましくは０．５ｃｍ３／ｇ以上である。また、窒素吸着法によって測定される、０．４〜５０ｎｍの範囲の細孔径の細孔容積が、全細孔容積に対して、５０％以上が好ましく、より好ましくは８０％以上である。多孔質シェル層４のメソ細孔の細孔容積を上記範囲とすることにより、汚染物質等の反応物の通過が阻害されない。 Particularly preferred porous shell layer 4 has a pore volume of pores (micropores and mesopores) having a pore diameter in the range of 0.4 to 50 nm, more preferably 0.1 cm 3 / g or more. Is 0.5 cm 3 / g or more. Further, the pore volume having a pore diameter in the range of 0.4 to 50 nm as measured by the nitrogen adsorption method is preferably 50% or more, more preferably 80% or more with respect to the total pore volume. By setting the pore volume of the mesopores of the porous shell layer 4 within the above range, passage of reactants such as contaminants is not inhibited.
多孔質シェル層４の厚さは、上記同様、多孔質シェル層４外から汚染物質、臭い、汚水、微生物等を通過させ、また、紫外光をコア部１まで到達させ、しかも多孔質シェル層４自体が耐久性を有する限り如何なる大きさであっても良い。上記条件を考慮すると、多孔質シェル層４の厚さは、１０ｎｍ〜１μｍの範囲にあることが好ましい。 As with the above, the thickness of the porous shell layer 4 is such that contaminants, odors, sewage, microorganisms, etc. pass from the outside of the porous shell layer 4, and ultraviolet light reaches the core portion 1. As long as 4 itself has durability, it may be any size. Considering the above conditions, the thickness of the porous shell layer 4 is preferably in the range of 10 nm to 1 μm.
多孔質シェル層４は、多孔性（酸化物）組織を形成可能であれば、如何なる原料を使用しても良い。多孔質組織を良好に形成することができるものとして、金属アルコキシド、金属アセチルアセテート、金属硝酸塩、若しくは金属塩酸塩が挙げられる。
好ましい金属アルコキシドの具体例としては、シリコンアルコキシド、ジルコニウムアルコキシド、アルミニウムアルコキシド、マグネシウムアルコキシド、ランタンアルコキシド、セリウムアルコキシドが挙げられる。また、好ましい金属アセチルアセテートの具体例としては、ジルコニウムアセチルアセテート、マグネシウムアセチルアセテート、及びセリウムアセチルアセテートが挙げられる。さらに、好ましい金属硝酸塩の具体例としては、硝酸ランタン、及び硝酸セリウムが挙げられ、好ましい金属塩酸塩の具体例としては、塩化ジルコニウム、塩化マグネシウム、及び塩化セリウムが挙げられる。
As long as the porous shell layer 4 can form a porous (oxide) structure, any raw material may be used. Metal alkoxides, metal acetyl acetates, metal nitrates, or metal hydrochlorides can be cited as examples that can form a porous structure satisfactorily.
Specific examples of preferable metal alkoxide include silicon alkoxide, zirconium alkoxide, aluminum alkoxide, magnesium alkoxide, lanthanum alkoxide, and cerium alkoxide. Specific examples of preferable metal acetyl acetates include zirconium acetyl acetate, magnesium acetyl acetate, and cerium acetyl acetate. Furthermore, specific examples of preferred metal nitrates include lanthanum nitrate and cerium nitrate, and specific examples of preferred metal hydrochlorides include zirconium chloride, magnesium chloride, and cerium chloride.
したがって、本発明に係る多孔質シェル層４は、例えば酸化珪素、酸化アルミニウム、酸化ジルコニウム、酸化マグネシウム、酸化ランタン及び酸化セリウムからなる群から選択される少なくとも一種を含む。また、多孔質シェル層４は、上記酸化物のうち異なる２以上の酸化物により形成されていてもよい。 Therefore, the porous shell layer 4 according to the present invention includes at least one selected from the group consisting of, for example, silicon oxide, aluminum oxide, zirconium oxide, magnesium oxide, lanthanum oxide, and cerium oxide. The porous shell layer 4 may be formed of two or more different oxides among the above oxides.
（実施の形態２）
〈光触媒の作製方法〉
本発明の実施の形態２に係る光触媒の作製方法では、細孔形成剤として水溶性ポリマーを用いる。
細孔形成剤として水溶性ポリマーを用いた場合、実施の形態１における３の工程（細孔形成剤の混合工程）において、水溶性ポリマーで炭素含有層２’の表面が被覆され炭素含有層２’上に水溶性ポリマーの層３が形成されるとともに、当該溶媒中に水溶性ポリマーが分散される。ここで、水溶性ポリマーを例示すれば、ポリビニルピロリドン、ポリビニルアルコール、ポリエチレンイミン、ポリエチレンオキシド、ポリアクリル酸、ポリアクリルアミド、ポリアルキルアミン等が挙げられる。また、水溶性ポリマーとしてトリブロックコポリマーを使用することもできる。当該トリブロックコポリマーとしては、具体的には、エチレンオキシド-プロピレンオキシド-エチレンオキシド等が挙げられる。これらのポリマーは、炭素含有層と多孔質シェル層前駆物質との親和性を高めることができるだけでなく、多孔質シェル層の細孔形成にも寄与しているものと考えられる。
(Embodiment 2)
<Method for producing photocatalyst>
In the method for producing a photocatalyst according to Embodiment 2 of the present invention, a water-soluble polymer is used as the pore forming agent.
When a water-soluble polymer is used as the pore-forming agent, the surface of the carbon-containing layer 2 ′ is coated with the water-soluble polymer in the step 3 (pore-forming agent mixing step) in Embodiment 1, and the carbon-containing layer 2 A layer 3 of a water-soluble polymer is formed thereon, and the water-soluble polymer is dispersed in the solvent. Examples of water-soluble polymers include polyvinyl pyrrolidone, polyvinyl alcohol, polyethyleneimine, polyethylene oxide, polyacrylic acid, polyacrylamide, and polyalkylamine. Moreover, a triblock copolymer can also be used as a water-soluble polymer. Specific examples of the triblock copolymer include ethylene oxide-propylene oxide-ethylene oxide. These polymers are considered to not only increase the affinity between the carbon-containing layer and the porous shell layer precursor, but also contribute to the formation of pores in the porous shell layer.
また、実施の形態１における４の工程（多孔質シェル層の形成工程）では、上記の懸濁液に、多孔質シェル層の前駆物質、例えばＴＥＯＳを混合することにより、多孔質シェル層４が、炭素含有層の表面を被覆する水溶性ポリマーの層３を起点として、上記懸濁液に分散された水溶性ポリマーを取り込みながら成長する。そのため、当該水溶性ポリマー分子の大きさに応じた細孔を多孔質シェル層４に設けることができる。
他の工程に関しては、実施の形態１に係る光触媒の作製方法と同様である。
In the step 4 (formation step of the porous shell layer) in the first embodiment, the porous shell layer 4 is formed by mixing a precursor of the porous shell layer, for example, TEOS, with the above suspension. From the water-soluble polymer layer 3 that covers the surface of the carbon-containing layer, the growth starts while taking in the water-soluble polymer dispersed in the suspension. Therefore, pores corresponding to the size of the water-soluble polymer molecule can be provided in the porous shell layer 4.
The other steps are the same as the photocatalyst manufacturing method according to the first embodiment.
（実施の形態３）
〈光触媒の作製方法〉
本発明の実施の形態３に係る光触媒の作製方法では、細孔形成剤として有機官能基を１つ以上含む金属アルコキシドを用いる。
本発明の実施の形態３に係る光触媒の作製方法は、１．コア部に含まれる光触媒粒子を準備する工程（光触媒粒子の準備工程）と、２．コア部の表面の少なくとも一部に直接炭素含有層を形成する工程（炭素含有層の形成工程）と、３．炭素含有層が形成されたコア部を懸濁させた溶媒に表面処理剤を混合して、前記炭素含有層の表面を表面処理剤で被覆する工程（表面処理工程）と、４．溶媒中に細孔形成剤及び多孔質シェル層の前駆物質を混合して、前記表面処理剤の層上に、細孔形成剤を含んでなる多孔質シェル層となる層を形成する工程（多孔質シェル層の形成工程）と、５．コア部と多孔質シェル層となる層との間にある前記炭素含有層及び前記表面処理剤の層並びに前記多孔質シェル層となる層の壁内に含まれる細孔形成剤を除去する工程（炭素含有層、表面処理剤及び細孔形成剤の除去工程）と、を含み、必要に応じて、６．光触媒を水素雰囲気下で熱処理し還元処理する工程（活性化処理工程）をさらに含んでいてもよい。ここで、１、２、５、６の工程については、実施の形態１における工程と同様であるため省略する。
３．表面処理工程
本実施の形態３に係る光触媒の作製方法では、２の工程、すなわち炭素含有層の形成工程において炭素含有層が形成されたコア部の表面を、塩基性官能基をもつ表面処理剤、例えばアミノ基一つ以上含む金属アルコキシド、好ましくはシリコンアルコキシドで処理し、炭素含有層表面にこれを吸着させる。これにより、次の４の工程において、炭素含有層の表面に例えばオクタデシル基（Ｃ１８Ｈ３７−）を含む均一なシリカ層を形成させることができる。
ここで、塩基性官能基を一つ以上含むシリコンアルコキシドとしては、アミノエチルアミノプロピルトリメキシシラン（ＡＥＡＰ）、アミノエチルアミノプロピルメチルジメキシシラン、アミノエチルアミノウンデシルトリメキシシラン、アミノフェニルトリメトキシシラン、アミノプロピルジメチルエトキシシラン、アミノプロピルメチルジエトキシシラン、アミノプロピルトリエトキシシラン、アミノプロピルトリメトキシシラン、が挙げられる。これらを炭素含有層の表面に吸着させると、アミノ基の触媒作用によって式Ｖの脱水縮合反応を炭素含有層の表面で効果的に進行させることができる。アミノ基の効果としてはほかに、これがカチオン性であるため、炭素含有層の最外表面は正の電荷を帯びており、多孔質シェル層の前駆物質は上記のアミノ基を表面にもつ炭素含有層に引きつけられやすくなることが考えられる。
表面処理工程及びその後の多孔質シェル層の形成工程で使用される溶媒としては、エタノール等のアルコールやアセトニトリル等の有機溶媒や水溶媒等が挙げられる。
４．多孔質シェル層の形成工程
続いて４．多孔質シェル層の形成工程において、多孔質シェル層の前駆物質と細孔形成剤とを含む溶液中に炭素含有層被覆光触媒粒子を懸濁させて、これらを加水分解および脱水縮合させる。ここで、本実施の形態に係る細孔形成剤として、有機官能基を含む金属アルコキシド若しくは有機官能基を含む金属クロライドを用いる。これらは、当該有機官能基が後の工程で除去されるため細孔形成に寄与する一方、多孔質シェル層を構成するアルコキシド等を含むため多孔質シェル層の前駆物質としての役割をも果たす。
以下、多孔質シェル層の前駆物質として、ＴＥＯＳを、細孔形成剤として、ＯＤＴＳを使用した場合について説明する。
まず、下記式IIIに従って、ＯＤＴＳを加水分解しオクタデシル基を備えるＳｉ（ＯＨ）３（Ｃ１８Ｈ３７）を生成する。また、上記反応と前後して、下記式IＶに従って、ＴＥＯＳを加水分解しＳｉ(ＯＨ)４を生成する。これらは、式Ｖに従ってその水酸基同士が脱水縮合反応することにより結合する。これにより、架橋構造が成長しシリカ層が形成される。
(Embodiment 3)
<Method for producing photocatalyst>
In the method for producing a photocatalyst according to Embodiment 3 of the present invention, a metal alkoxide containing one or more organic functional groups is used as a pore forming agent.
A method for producing a photocatalyst according to Embodiment 3 of the present invention is as follows. 1. a step of preparing photocatalyst particles contained in the core part (a step of preparing photocatalyst particles); 2. a step of directly forming a carbon-containing layer on at least a part of the surface of the core part (a step of forming a carbon-containing layer); 3. a step (surface treatment step) of coating the surface of the carbon-containing layer with a surface treatment agent by mixing a surface treatment agent in a solvent in which the core portion on which the carbon-containing layer is formed is suspended; A step of mixing a pore forming agent and a porous shell layer precursor in a solvent to form a layer to be a porous shell layer containing the pore forming agent on the surface treatment agent layer (porous 4. a step of forming a porous shell layer); Removing the pore-forming agent contained in the walls of the carbon-containing layer and the surface treatment agent layer and the layer to be the porous shell layer between the core portion and the layer to be the porous shell layer ( And a carbon-containing layer, a surface treatment agent and a pore forming agent removal step), and if necessary, 6. There may be further included a step (activation treatment step) of subjecting the photocatalyst to a heat treatment under a hydrogen atmosphere and a reduction treatment. Here, the steps 1, 2, 5, and 6 are the same as the steps in the first embodiment, and thus are omitted.
3. Surface treatment step In the photocatalyst production method according to the third embodiment, the surface treatment agent having a basic functional group is formed on the surface of the core part on which the carbon-containing layer is formed in the second step, that is, the carbon-containing layer formation step. For example, it is treated with a metal alkoxide containing one or more amino groups, preferably silicon alkoxide, and adsorbed on the surface of the carbon-containing layer. Thereby, in the next four steps, a uniform silica layer containing, for example, an octadecyl group (C 18 H 37 —) can be formed on the surface of the carbon-containing layer.
Here, as the silicon alkoxide containing one or more basic functional groups, aminoethylaminopropyltrimexylsilane (AEAP), aminoethylaminopropylmethyldimethyloxysilane, aminoethylaminoundecyltrimexylsilane, aminophenyltrimethoxy Examples thereof include silane, aminopropyldimethylethoxysilane, aminopropylmethyldiethoxysilane, aminopropyltriethoxysilane, and aminopropyltrimethoxysilane. When these are adsorbed on the surface of the carbon-containing layer, the dehydration condensation reaction of Formula V can be effectively advanced on the surface of the carbon-containing layer by the catalytic action of the amino group. Another effect of the amino group is that since it is cationic, the outermost surface of the carbon-containing layer has a positive charge, and the precursor of the porous shell layer contains the above-mentioned amino group-containing carbon. It may be easier to be attracted to the layer.
Examples of the solvent used in the surface treatment step and the subsequent formation step of the porous shell layer include alcohols such as ethanol, organic solvents such as acetonitrile, and water solvents.
4). 3. Step of forming porous shell layer In the step of forming the porous shell layer, the carbon-containing layer-coated photocatalyst particles are suspended in a solution containing the precursor of the porous shell layer and the pore forming agent, and these are hydrolyzed and dehydrated and condensed. Here, as the pore forming agent according to the present embodiment, a metal alkoxide containing an organic functional group or a metal chloride containing an organic functional group is used. These contribute to pore formation because the organic functional group is removed in a later step, and also serve as a precursor of the porous shell layer because they contain alkoxide and the like constituting the porous shell layer.
Hereinafter, the case where TEOS is used as the precursor of the porous shell layer and ODTS is used as the pore forming agent will be described.
First, according to the following formula III, ODTS is hydrolyzed to produce Si (OH) 3 (C 18 H 37 ) having an octadecyl group. Also, before and after the above reaction, TEOS is hydrolyzed to produce Si (OH) 4 according to the following formula IV. According to Formula V, these hydroxyl groups are bonded together by a dehydration condensation reaction. Thereby, a crosslinked structure grows and a silica layer is formed.
ここで、シリコンアルコキシドに含まれるアルキル基は、分子内に２つ以上あっても良く、直鎖状であってもまたは分岐状であっても良い。またアルキル基の末端や中間に官能基等を含むものでも良い。直鎖または分岐状のアルキル基の代表例として、メチル基、エチル基、ｎ−プロピル基、イソプロピル基、ｎ−ブチル基、ｓｅｃ−ブチル基、ｔｅｒｔ−ブチル基、ペンチル基、ヘキシル基、オクチル基、イソオクチル基、オクタデシル基等が挙げられ、含まれる官能基等の代表例として、フェニル基、ナフチル基、オクテニル基、ビニル基、アミノアルキル基、アミノフェニル基、アセトキシアルキル基、アクリロキシ基、アリル基、アリルアミノ基、アミノエチルアミノプロピル基、ブロモアルキル基、クロロアルキル基、シアノアルキル基、シクロヘキシル基、メタクリルオキシプロピル基フルオロアルキル基、フルオロフェニル基、メルカプトプロピル基、アミノ基、アセトキシ基、ブロモ基、クロロ基、シアノ基、シクロヘキシル基、メタクリルオキシプロピル基、フルオロ基、メルカプト基等が挙げられる。また、メトキシ基についても少なくとも一つが、エトキシ基、ブトキシ基などで一部置換されていてもよい。 Here, two or more alkyl groups contained in the silicon alkoxide may be present in the molecule, and may be linear or branched. Moreover, the thing containing a functional group etc. in the terminal and middle of an alkyl group may be sufficient. Typical examples of linear or branched alkyl groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, pentyl, hexyl, and octyl. , Isooctyl group, octadecyl group and the like, and representative examples of the functional group and the like include phenyl group, naphthyl group, octenyl group, vinyl group, aminoalkyl group, aminophenyl group, acetoxyalkyl group, acryloxy group, allyl group , Allylamino group, aminoethylaminopropyl group, bromoalkyl group, chloroalkyl group, cyanoalkyl group, cyclohexyl group, methacryloxypropyl group fluoroalkyl group, fluorophenyl group, mercaptopropyl group, amino group, acetoxy group, bromo group, Chloro group, cyano group, cyclohexyl , Methacryloxypropyl group, fluoro group, a mercapto group, and the like. Further, at least one of the methoxy groups may be partially substituted with an ethoxy group, a butoxy group, or the like.
アルキル基等の官能基を含むシリコンアルコキシドを用いた場合、官能基が残ったまま加水分解反応及び脱水縮合反応が進行する。以下にＴＥＯＳ及びＯＤＴＳ（オクタデシルトリメトキシシラン、Ｓｉ（ＯＣＨ３）３（Ｃ１８Ｈ３７））の加水分解反応及び脱水縮合反応の一例を示す。
III．ＯＤＴＳの加水分解反応
Ｓｉ（ＯＣＨ３）３（Ｃ１８Ｈ３７）＋３Ｈ２Ｏ→Ｓｉ（ＯＨ）３（Ｃ１８Ｈ３７）＋３ＣＨ３ＯＨ
IＶ．ＴＥＯＳの加水分解反応
Ｓｉ(ＯＣ２Ｈ５)４＋４Ｈ２Ｏ→Ｓｉ(ＯＨ)４＋４Ｃ２Ｈ５ＯＨ
Ｖ．脱水縮合反応
Ｓｉ（ＯＨ）３（Ｃ１８Ｈ３７）＋Ｓｉ(ＯＨ)４→（Ｃ１８Ｈ３７）（ＯＨ）２Ｓｉ−Ｏ−Ｓｉ（ＯＨ）３＋Ｈ２Ｏ
（Ｃ１８Ｈ３７）（ＯＨ）２Ｓｉ−Ｏ−Ｓｉ（ＯＨ）３＋Ｓｉ（ＯＨ）３（Ｃ１８Ｈ３７）→（Ｃ１８Ｈ３７）（ＯＨ）２Ｓｉ−Ｏ−Ｓｉ（ＯＨ）２−Ｏ−Ｓｉ（ＯＨ）２（Ｃ１８Ｈ３７）
When a silicon alkoxide containing a functional group such as an alkyl group is used, a hydrolysis reaction and a dehydration condensation reaction proceed with the functional group remaining. Examples of hydrolysis reaction and dehydration condensation reaction of TEOS and ODTS (octadecyltrimethoxysilane, Si (OCH 3 ) 3 (C 18 H 37 )) are shown below.
III. Hydrolysis reaction of ODTS Si (OCH 3 ) 3 (C 18 H 37 ) + 3H 2 O → Si (OH) 3 (C 18 H 37 ) + 3CH 3 OH
IV. Hydrolysis reaction of TEOS Si (OC 2 H 5 ) 4 + 4H 2 O → Si (OH) 4 + 4C 2 H 5 OH
V. Dehydration condensation reaction Si (OH) 3 (C 18 H 37 ) + Si (OH) 4 → (C 18 H 37 ) (OH) 2 Si—O—Si (OH) 3 + H 2 O
(C 18 H 37) (OH ) 2 Si-O-Si (OH) 3 + Si (OH) 3 (C 18 H 37) → (C 18 H 37) (OH) 2 Si-O-Si (OH) 2 —O—Si (OH) 2 (C 18 H 37 )
前記反応によりオクタデシル基（Ｃ１８Ｈ３７−）を含むシリカ層が形成され、シリカ層に含まれる、細孔形成剤の一部であるオクタデシル基の部分が加熱により分解除去され、この部分が細孔となる。本実施の形態３に係る方法では、実施の形態１又は２に係る方法と同様、ミクロ孔及びメソ孔を多く含む多孔質シェル層を形成することができる。
他の工程に関しては、実施の形態１に係る光触媒の作製方法と同様である。また、細孔形成剤の有機官能基の種類を変化させることにより、最終製品に係る光触媒の多孔質シェル層の細孔径を調整することができ、また、細孔形成剤の濃度を調整することにより多孔質シェル層の気孔率を調整することもできる。
The reaction by octadecyl (C 18 H 37 -) is a silica layer is formed containing, contained in the silica layer, portions of the octadecyl groups are decomposed and removed by heating a part of the pore former, this part fine It becomes a hole. In the method according to the third embodiment, a porous shell layer including many micropores and mesopores can be formed as in the method according to the first or second embodiment.
The other steps are the same as the photocatalyst manufacturing method according to the first embodiment. In addition, by changing the type of organic functional group of the pore forming agent, the pore diameter of the porous shell layer of the photocatalyst according to the final product can be adjusted, and the concentration of the pore forming agent can be adjusted. Thus, the porosity of the porous shell layer can be adjusted.
（使用の形態１）
続いて、本発明に係る光触媒の使用態様に関して詳細に説明する。
本発明の光触媒は、バインダーとともに、溶媒に分散して塗料組成物とすることができる。バインダーとしては、アクリル樹脂、エポキシ樹脂、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、フッ素系樹脂、シリコーン系樹脂、水ガラス、コロイダルシリカ、オルガノポリシロキサン、セメント、セッコウなどの汎用のバインダーを用いることができる。前記の溶媒としては、水やトルエン、アルコールなどの有機溶媒を用いることができる。塗料組成物中の光触媒の量は適宜設定することができるが、光触媒とバインダーとの合量に対する容積基準として、セメントまたはセッコウを用いる場合には、光触媒の含有量は５〜４０％が好ましく、５〜２５％がより好ましい。また、セメント、セッコウ以外のバインダーを用いる場合には、光触媒の含有量は好ましくは５〜９８％、より好ましくは２０〜９８％、さらに好ましくは５０〜９８％である。塗料組成物には、架橋剤、分散剤、充填剤などを配合させても良い。架橋剤としては、イソシアネート系、メラミン系などの通常の架橋剤を、分散剤としては、カップリング剤などを使用することができる。
前記の塗料組成物を基体に塗布あるいは吹き付けて、光触媒を含有する塗膜を形成する。例えば、含浸法、ディップコーティング法、スピナーコーティング法、ブレードコーティング法、ローラーコーティング法、ワイヤーバーコーティング法、リバースロールコーティング法などの通常の方法で塗布したり、あるいは、スプレーコーティング法などの通常の方法で吹き付け、乾燥あるいは焼成して、塗膜を形成する。基体としては、セラミックス、ガラスなどの無機材質の物品、プラスチック、ゴム、木、紙などの有機材質の物品、アルミニウムなどの金属、鋼などの合金などの金属材質の物品を用いることができ、基体の大きさや形には特に制限されない。
（使用の形態２）
また、本発明の光触媒は、紙、繊維、プラスチック等に含有させることができる。紙に含有させるには、光触媒を抄紙液に分散させて抄紙したり、抄紙した紙に光触媒を分散した液や前記の塗料組成物を塗布あるいは吹付けることもできる。繊維に含有させるには、繊維を製造する際に光触媒を原料液に含有させて重合して繊維を製造したり、製造した繊維に光触媒を分散した液や前記の塗料組成物を塗布あるいは吹付けることもできる。また、プラスチックに含有するには、プラスチック成形の際に含有させたり、成形したプラスチックの表面に、光触媒を分散した液や前記の塗料組成物を塗布あるいは吹付けることもできる。
（使用方法）
本発明の光触媒あるいは光触媒を含有した塗膜、紙、繊維、プラスチック等は、その回りに存在する被処理対象物、例えば有害物質、悪臭物質、油分、菌類などを吸着することができる。
また、本発明の光触媒あるいは光触媒を含有した塗膜、紙、繊維、プラスチック等に、その光触媒粒子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させることにより、その回りに存在する被処理対象物、例えば有害物質、悪臭物質、油分などを分解して浄化したり、殺菌したりすることができる。照射する光としては、紫外線を含有した光などが挙げられ、例えば、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。また、可視光応答型光触媒粒子の場合は、可視光を含む光を用いることができる。光の照射量や照射時間などは処理する物質の量などによって適宜設定できる。
(Usage form 1)
Then, the usage aspect of the photocatalyst concerning this invention is demonstrated in detail.
The photocatalyst of the present invention can be dispersed in a solvent together with a binder to obtain a coating composition. As the binder, general-purpose binders such as acrylic resin, epoxy resin, polyester resin, melamine resin, urethane resin, alkyd resin, fluorine resin, silicone resin, water glass, colloidal silica, organopolysiloxane, cement, gypsum are used. be able to. As said solvent, organic solvents, such as water, toluene, alcohol, can be used. The amount of the photocatalyst in the coating composition can be appropriately set, but when using cement or gypsum as a volume standard with respect to the total amount of the photocatalyst and the binder, the content of the photocatalyst is preferably 5 to 40%, 5 to 25% is more preferable. Moreover, when using binders other than cement and gypsum, content of a photocatalyst becomes like this. Preferably it is 5-98%, More preferably, it is 20-98%, More preferably, it is 50-98%. In the coating composition, a crosslinking agent, a dispersant, a filler and the like may be blended. As the crosslinking agent, an ordinary crosslinking agent such as isocyanate or melamine can be used, and as the dispersing agent, a coupling agent or the like can be used.
The coating composition is applied or sprayed on the substrate to form a coating film containing a photocatalyst. For example, it is applied by a normal method such as an impregnation method, a dip coating method, a spinner coating method, a blade coating method, a roller coating method, a wire bar coating method, a reverse roll coating method, or a normal method such as a spray coating method. Sprayed, dried or fired to form a coating film. As the substrate, an inorganic material such as ceramics and glass, an organic material such as plastic, rubber, wood and paper, a metal such as aluminum, and an alloy such as steel can be used. There are no particular restrictions on the size or shape of the.
(Type of use 2)
In addition, the photocatalyst of the present invention can be contained in paper, fiber, plastic and the like. For inclusion in paper, the photocatalyst may be dispersed in a papermaking liquid to make paper, or the liquid in which the photocatalyst is dispersed and the coating composition described above may be applied or sprayed on the papermaking paper. In order to make it contain in a fiber, when manufacturing a fiber, a photocatalyst is made to contain in a raw material liquid, and a fiber is manufactured, or the liquid which disperse | distributed the photocatalyst and the said coating composition are apply | coated or sprayed on the manufactured fiber. You can also. In addition, when it is contained in plastic, it can be contained during plastic molding, or a liquid in which a photocatalyst is dispersed or the coating composition can be applied or sprayed on the surface of the molded plastic.
(how to use)
The photocatalyst of the present invention or a coating film, paper, fiber, plastic or the like containing the photocatalyst can adsorb objects to be treated, such as harmful substances, malodorous substances, oils, fungi, and the like present therearound.
In addition, by irradiating the photocatalyst of the present invention or a coating film, paper, fiber, plastic, etc. containing the photocatalyst with light having a wavelength that has an energy equal to or greater than the band gap of the photocatalytic particle, Substances such as harmful substances, malodorous substances, oils and the like can be decomposed and purified or sterilized. Examples of the light to be irradiated include light containing ultraviolet rays. For example, light from sunlight, a fluorescent lamp, a black light, a halogen lamp, a xenon flash lamp, a mercury lamp, or the like can be used. In the case of visible light responsive photocatalyst particles, light including visible light can be used. The light irradiation amount, irradiation time, and the like can be appropriately set depending on the amount of the substance to be processed.
続いて、本発明に係る光触媒の作製方法により光触媒を作製し、これについて評価実験を行った。
１．光触媒の作製
まず、石原産業株式会社製の光触媒用酸化チタン（ＴｉＯ２:ＳＴ-４１）を０．５Ｍグルコース水溶液に懸濁させ、これを１８０℃で６時間水熱処理して、炭素被覆ＴｉＯ２（以下、ｃ／ＴｉＯ２と称する。ここで、ｃ／とは、炭素の層で被覆していることを意味している。）とした。その後、この炭素被覆ＴｉＯ２ １ｇとをセチルトリメチルアンモニウムブロミド（ＣＴＡＢ） ０．５ｇとを水溶液に懸濁させ、ＴｉＯ２上に形成された炭素の層の表面をＣＴＡＢで被覆した（ＣＴＡＢ／ｃ／ＴｉＯ２）。その後、上記懸濁液にテトラエトキシシラン（ＴＥＯＳ）８ｍｌを注入することにより、炭素の層の表面を被覆したＣＴＡＢを基点としてＴＥＯＳの加水分解・縮合物であるシリカを析出させた（Ｓｉ／ｃ／ＴｉＯ２と称する。ここで、Ｓｉ／ｃ／とは、炭素の層で被覆した後、その炭素の層をシリカの層で被覆していることを意味している。）後、空気中において６００℃で３時間熱処理して炭素の層とＣＴＡＢを除去し、中空状ポーラスシリカ被覆ＴｉＯ２（ｐ−Ｓｉ／／ＴｉＯ２と称する。ここで、ｐ−Ｓｉはポーラス状（多孔質）のシリカを意味し、また、／／はｐ−ＳｉとＴｉＯ２との間に中空層が介在することを意味する。）を得た。このようにして得られた光触媒（ｐ−Ｓｉ／／ＴｉＯ２）のＳＥＭ写真を図４に示す。図４から分かるように、多孔質シェル層の内側に光触媒粒子が見られた。多孔質シェル層と光触媒粒子との間には中空層が介在するのが分かる。また、多孔質シェル層の壁内には、微小なポーラス構造が見られこれがミクロ細孔、メソ細孔を構成するものと考えられる。
また、このようにして得られたｐ−Ｓｉ／／ＴｉＯ２について吸着特性を調べた。吸着特性を調べるために、窒素吸着測定を用いた。図５ａに、窒素吸着等温線を示す。等温線は期待通りメソ細孔をもつ粉体に特徴的なIV型を示した。IV型とは、吸着平衡圧を順次増加（吸着）して得られる吸着量と、平衡圧を順次減少（脱着）させて得られる吸着量とが異なる場合（ヒステリシスをもつという）の等温線であり、メソ細孔の存在を示す。実際、等温線からメソ細孔のサイズ分布を算出する一般的な解析法であるＢＪＨ法に基づいて、細孔サイズ分布をプロットすると、図５ｂに示すように、ｐ−Ｓｉ／／ＴｉＯ２は３ｎｍを中心とする発達した細孔をもつことがわかる。
Subsequently, a photocatalyst was produced by the photocatalyst production method according to the present invention, and an evaluation experiment was performed.
1. Preparation of photocatalyst First, titanium oxide for photocatalyst (TiO 2 : ST-41) manufactured by Ishihara Sangyo Co., Ltd. was suspended in a 0.5 M aqueous glucose solution, and this was hydrothermally treated at 180 ° C. for 6 hours to obtain carbon-coated TiO 2. (Hereinafter referred to as c / TiO 2 , where c / means covering with a carbon layer). Thereafter, 1 g of this carbon-coated TiO 2 and 0.5 g of cetyltrimethylammonium bromide (CTAB) were suspended in an aqueous solution, and the surface of the carbon layer formed on TiO 2 was coated with CTAB (CTAB / c / TiO 2). Thereafter, 8 ml of tetraethoxysilane (TEOS) was injected into the suspension, thereby precipitating silica, which is a hydrolysis / condensation product of TEOS, based on CTAB covering the surface of the carbon layer (Si / c / TiO 2 , where Si / c / means that the carbon layer is coated with a silica layer, and then the carbon layer is coated with a silica layer. A heat treatment is performed at 600 ° C. for 3 hours to remove the carbon layer and CTAB, and the hollow porous silica-coated TiO 2 (referred to as p-Si // TiO 2. Here, p-Si is porous (porous) silica. And // means that a hollow layer is interposed between p-Si and TiO 2 ). An SEM photograph of the photocatalyst (p-Si // TiO 2 ) thus obtained is shown in FIG. As can be seen from FIG. 4, photocatalyst particles were observed inside the porous shell layer. It can be seen that a hollow layer is interposed between the porous shell layer and the photocatalyst particles. In addition, a minute porous structure is observed in the wall of the porous shell layer, which is considered to constitute micropores and mesopores.
Further, the adsorption characteristics of the p-Si // TiO 2 thus obtained were examined. Nitrogen adsorption measurements were used to examine adsorption properties. FIG. 5a shows the nitrogen adsorption isotherm. The isotherm showed the type IV characteristic of powder with mesopores as expected. Type IV is an isotherm when the adsorption amount obtained by sequentially increasing (adsorbing) the adsorption equilibrium pressure is different from the adsorption amount obtained by sequentially decreasing (desorbing) the equilibrium pressure (having hysteresis). Yes, indicating the presence of mesopores. In fact, when the pore size distribution is plotted based on the BJH method, which is a general analysis method for calculating the mesopore size distribution from the isotherm, p-Si // TiO 2 is as shown in FIG. It can be seen that it has developed pores centered at 3 nm.
２．比較試験
続いて、上述のようにして得られた光触媒を用いて、性能比較試験を行った。比較例としては、ポーラスシリカ層で被覆されていない、裸のままの光触媒（ＳＴ−４１）と、ポーラスシリカ層で直接被覆された光触媒（ｐ−Ｓｉ／ＴｉＯ２と称する。）と、を用いた。ポーラスシリカ層で直接被覆された光触媒（ｐ−Ｓｉ／ＴｉＯ２）は以下のようにして作製した。
2. Comparative Test Subsequently, a performance comparative test was performed using the photocatalyst obtained as described above. As a comparative example, a bare photocatalyst (ST-41) not covered with a porous silica layer and a photocatalyst (referred to as p-Si / TiO 2 ) directly covered with a porous silica layer are used. It was. The photocatalyst (p-Si / TiO 2 ) directly coated with the porous silica layer was prepared as follows.
まず、石原産業株式会社製の光触媒用酸化チタン（ＴｉＯ２:ＳＴ-４１）をセチルトリメチルアンモニウムブロミド（ＣＴＡＢ）水溶液に懸濁させた（ＣＴＡＢ／ＴｉＯ２）。その後、上記懸濁液にテトラエトキシシラン（ＴＥＯＳ）を注入することにより、ＣＴＡＢのミセルを基点としてＴＥＯＳの加水分解・縮合物であるシリカを析出させた（Ｓｉ／ＴｉＯ２と称する。ここで、Ｓｉ／とは、シリカの層で被覆されていることを意味している。）後、６００℃で３時間熱処理をして、ポーラスシリカ被覆ＴｉＯ２（ｐ−Ｓｉ／ＴｉＯ２と称する。ここで、ｐ−Ｓｉはポーラス状（多孔質）のシリカを意味し、また、ｐ−Ｓｉ／ＴｉＯ２とはポーラス状のシリカにより直接被覆されたＴｉＯ２を意味する。）を得た。 First, titanium oxide for photocatalyst (TiO 2 : ST-41) manufactured by Ishihara Sangyo Co., Ltd. was suspended in an aqueous solution of cetyltrimethylammonium bromide (CTAB) (CTAB / TiO 2 ). Thereafter, tetraethoxysilane (TEOS) was injected into the suspension, thereby precipitating silica as a hydrolysis / condensation product of TEOS from the CTAB micelle (referred to as Si / TiO 2) . Si / means that it is coated with a layer of silica.) After that, heat treatment is performed at 600 ° C. for 3 hours, and porous silica-coated TiO 2 (referred to as p-Si / TiO 2) . , P-Si means porous (porous) silica, and p-Si / TiO 2 means TiO 2 directly coated with porous silica).
（１）ＸＲＦ分析
まず、本発明に係るｐ−Ｓｉ／／ＴｉＯ２と従来例に係るｐ−Ｓｉ／ＴｉＯ２とをＸＲＦ分析した。ｐ−Ｓｉ／／ＴｉＯ２またはｐ−Ｓｉ／ＴｉＯ２をペレット状に成形し、蛍光X線測定装置（リガク社製、ＲＩＸ−３０００）により化学組成分析を行い、試料に含まれるＳｉＯ２の質量％を測定した。
(1) XRF analysis First, a p-Si / TiO 2 according to the conventional example with p-Si // TiO 2 according to the present invention has been XRF analysis. The p-Si // TiO 2 or p-Si / TiO 2 is formed into a pellet and subjected to chemical composition analysis using a fluorescent X-ray measurement apparatus (RIX-3000, manufactured by Rigaku Corporation). The mass of SiO 2 contained in the sample % Was measured.
表１に示すように、従来例に係るｐ−Ｓｉ／ＴｉＯ２では、サンプル中に占めるＳｉＯ２の質量％は４９．３ｗｔ％であったのに対し、本発明に係るｐ−Ｓｉ／／ＴｉＯ２では、７２．３ｗｔ％であった。 As shown in Table 1, in p-Si / TiO 2 according to the conventional example, the mass% of SiO 2 in the sample was 49.3 wt%, whereas p-Si // TiO according to the present invention was present. In 2 , it was 72.3 wt%.
（２）比表面積測定
続いて、本発明に係るｐ−Ｓｉ／／ＴｉＯ２と従来例に係るｐ−Ｓｉ／ＴｉＯ２と被覆されていない光触媒（ＳＴ−４１）の比表面積測定を行った。ｐ−Ｓｉ／／ＴｉＯ２またはｐ−Ｓｉ／ＴｉＯ２を１５０℃で３０分間脱気後、フローソーブ２３００（島津製作所）を用いて、窒素吸脱着を行い、比表面積を測定した。
(2) Following the specific surface area measurements were performed a specific surface area measurement of the p-Si // TiO 2 and according to the prior art p-Si / TiO 2 and uncoated photocatalyst according to the present invention (ST-41). After degassing p-Si // TiO 2 or p-Si / TiO 2 at 150 ° C. for 30 minutes, nitrogen adsorption / desorption was performed using Flowsorb 2300 (Shimadzu Corporation), and the specific surface area was measured.
表２に示すように、被覆のないＳＴ−４１では、比表面積は１０．２ｍ２／ｇであり、ｐ−Ｓｉ／ＴｉＯ２では、比表面積は４１３．２ｍ２／ｇであったのに対し、本発明に係るｐ−Ｓｉ／／ＴｉＯ２では、比表面積は５４３．６ｍ２／ｇであった。 As shown in Table 2, the specific surface area of the uncoated ST-41 was 10.2 m 2 / g, whereas the specific surface area of p-Si / TiO 2 was 413.2 m 2 / g. In p-Si // TiO 2 according to the present invention, the specific surface area was 543.6 m 2 / g.
（３）光触媒活性評価
続いて、上記の光触媒を用いて、大気中で光触媒活性の評価を行った。光触媒活性の評価は、光触媒により有機性ガスが分解され、当該有機性ガス濃度がどれだけ減少したかにより評価した。すなわち、有機性ガス濃度をより多く減少させた光触媒が、光触媒活性が高いと評価した。当該評価は、以下の条件で行った。
反応条件
反応ガス：アセトアルデヒド
初期濃度：１５０ｐｐｍ
評価系：閉鎖循環式
反応器体積：２．８Ｌ
循環速度：３Ｌ／ｍｉｎ
光源・照度：ブラックライト０．５ｍＷ／ｃｍ２
照射面積：２８．３ｃｍ２
触媒量：０．１ｇ
暗吸着：３０ｍｉｎ
光照射：６０ｍｉｎ
(3) Photocatalytic activity evaluation Subsequently, photocatalytic activity was evaluated in the atmosphere using the above-mentioned photocatalyst. The photocatalytic activity was evaluated based on how much the organic gas was decomposed by the photocatalyst and the organic gas concentration was reduced. That is, it was evaluated that a photocatalyst with a reduced organic gas concentration was high in photocatalytic activity. The evaluation was performed under the following conditions.
Reaction conditions Reaction gas: Acetaldehyde Initial concentration: 150 ppm
Evaluation system: closed circulation reactor volume: 2.8L
Circulation speed: 3L / min
Light source / illuminance: Black light 0.5 mW / cm 2
Irradiation area: 28.3 cm 2
Catalyst amount: 0.1 g
Dark adsorption: 30 min
Light irradiation: 60 min
図６に、本発明に係るｐ−Ｓｉ／／ＴｉＯ２とＳＴ−４１を用いた場合の、分解されずに残ったアセトアルデヒド濃度と時間との関係を示している。横軸を時間とし、縦軸をアセトアルデヒド濃度の対数としている。図６から分かるように、本発明に係るｐ−Ｓｉ／／ＴｉＯ２では、何も被覆していない光触媒（ＳＴ−４１）を用いた場合と同様の曲線となり、ポーラスシリカ層が被覆されていても光触媒活性に影響を与えないことが分かった。また、反応速度定数を算出すると、本発明に係るｐ−Ｓｉ／／ＴｉＯ２では、反応速度定数は２．０９（／ｈｏｕｒ）であるのに対し、被覆のないＳＴ−４１では、１．９６（／ｈｏｕｒ）であり、略同程度の反応速度を有することが分かった。 FIG. 6 shows the relationship between the concentration of acetaldehyde remaining undecomposed and time when p-Si // TiO 2 and ST-41 according to the present invention are used. The horizontal axis is time, and the vertical axis is the logarithm of acetaldehyde concentration. As can be seen from FIG. 6, in the p-Si // TiO 2 according to the present invention, a curve similar to the case of using a photocatalyst (ST-41) that is not coated with anything is formed, and the porous silica layer is coated. It was also found that it does not affect the photocatalytic activity. When the reaction rate constant is calculated, the reaction rate constant is 2.09 (/ hour) for p-Si // TiO 2 according to the present invention, whereas 1.96 for ST-41 without coating. (/ Hour), and it was found that the reaction rate was approximately the same.
したがって、ポーラスシリカ層で光触媒粒子を被覆する際中空層を介すれば、光触媒活性が低下しないことが分かった。 Therefore, it was found that the photocatalytic activity does not decrease when the photocatalyst particles are coated with the porous silica layer through the hollow layer.
また、図７に、従来例に係るｐ−Ｓｉ／ＴｉＯ２とＳＴ−４１を用いた場合のアセトアルデヒド濃度と時間との関係を示している。図７から分かるように、従来例に係るｐ−Ｓｉ／ＴｉＯ２では、何も被覆していない光触媒（ＳＴ−４１）より、光触媒活性が劣ることが分かる。 FIG. 7 shows the relationship between the acetaldehyde concentration and time when p-Si / TiO 2 and ST-41 according to the conventional example are used. As can be seen from FIG. 7, the p-Si / TiO 2 according to the conventional example is inferior in photocatalytic activity to the photocatalyst (ST-41) which is not coated with anything.
また、上記測定結果から反応速度定数を算出すると、従来例に係るｐ−Ｓｉ／ＴｉＯ２では、反応速度定数は０．９５（／ｈｏｕｒ）であるのに対し、被覆のないＳＴ−４１では、２．１３（／ｈｏｕｒ）であり、従来例に係るｐ−Ｓｉ／ＴｉＯ２を用いた場合の反応速度は、被覆のない光触媒（ＳＴ−４１）を用いた場合の反応速度の半分程度であることが分かった。 In addition, when calculating the reaction rate constant from the above measurement results, in p-Si / TiO 2 according to the conventional example, the reaction rate constant is 0.95 (/ hour), whereas in ST-41 without coating, 2.13 (/ hour), and the reaction rate when using p-Si / TiO 2 according to the conventional example is about half of the reaction rate when using a photocatalyst without coating (ST-41). I understood that.
したがって、直接ポーラスシリカ層で光触媒粒子を被覆すれば、光触媒の活性が著しく低下することが分かった。 Therefore, it was found that if the photocatalyst particles were directly coated with the porous silica layer, the activity of the photocatalyst was significantly reduced.
（４）塗膜耐光性評価
続いて、上記３種類の光触媒が塗膜に混合されたものを用いて耐光性評価を行った。図８は、本発明に係るｐ−Ｓｉ／／ＴｉＯ２と被覆のないＳＴ−４１が塗膜に混合されたものを用いた場合の、塗膜の色差と時間との関係を示しており、図９は、従来例に係るｐ−Ｓｉ／ＴｉＯ２と被覆のないＳＴ−４１が塗膜に混合されたものを用いた場合の、塗膜の色差と時間との関係を示している。塗膜耐光性評価は、光源としてブラックライトを用い、３ｍＷ／ｃｍ２の照度を用いた。３０、６０、９０、１２０、１８０分照射した際の色差を測定した。図８及び９から分かるように、被覆のないＳＴ−４１が塗膜に混合されたものを用いた場合、塗膜が直接光触媒粒子に接触するため、光照射時間とともに色差が増加する。それに対して、図８から分かるように、本発明に係るｐ−Ｓｉ／／ＴｉＯ２が塗膜に混合されたものを用いた場合、光照射時間が長くなっても色差の増加は見られなかった。また、図９から分かるように、従来例に係るｐ−Ｓｉ／ＴｉＯ２が塗膜に混合されたものを用いた場合も、光照射時間が長くなっても色差の増加は殆ど見られなかった。したがって、被覆のないＳＴ−４１では、被覆がないため、光触媒粒子が塗膜に直接接触するため、当該光触媒粒子によって塗膜が分解されたのに対し、ポーラスシリカ層で直接若しくは中空層を介して被覆されたｐ−Ｓｉ／ＴｉＯ２若しくはｐ−Ｓｉ／／ＴｉＯ２では、ポーラスシリカ層が光触媒粒子と塗膜との接触を防止するため、当該光触媒粒子によって塗膜が分解されなかったと考えられる。中空層の存否によっては、耐光性評価は影響を受けないことが分かる。
(4) Coating Film Light Resistance Evaluation Subsequently, light resistance evaluation was performed using the above-mentioned three kinds of photocatalysts mixed with the coating film. FIG. 8 shows the relationship between the color difference of the coating film and time when p-Si // TiO 2 according to the present invention and ST-41 without coating are mixed in the coating film, FIG. 9 shows the relationship between the color difference of the coating film and time when p-Si / TiO 2 according to the conventional example and ST-41 without coating are mixed in the coating film. The coating light resistance evaluation was performed using black light as a light source and an illuminance of 3 mW / cm 2 . The color difference when irradiated for 30, 60, 90, 120, 180 minutes was measured. As can be seen from FIGS. 8 and 9, when the uncoated ST-41 mixed with the coating film is used, the coating film directly contacts the photocatalyst particles, so that the color difference increases with the light irradiation time. On the other hand, as can be seen from FIG. 8, when p-Si // TiO 2 according to the present invention is used in the coating film, no increase in color difference is observed even when the light irradiation time is increased. It was. In addition, as can be seen from FIG. 9, even when the p-Si / TiO 2 according to the conventional example was mixed with the coating film, even if the light irradiation time was increased, the increase in color difference was hardly seen. . Therefore, in ST-41 without coating, since there is no coating, the photocatalyst particles are in direct contact with the coating film, so that the coating film was decomposed by the photocatalyst particles, whereas the porous silica layer directly or through the hollow layer. In p-Si / TiO 2 or p-Si // TiO 2 coated in this way, the porous silica layer prevents contact between the photocatalyst particles and the coating film, so it is considered that the coating film was not decomposed by the photocatalyst particles. . It can be seen that the light resistance evaluation is not affected by the presence or absence of the hollow layer.
（５）塗膜光触媒活性評価
上記の光触媒を用いて、塗膜中で光触媒活性の評価を行った。当該評価は、以下の条件で行った。
反応条件
反応ガス：アセトアルデヒド
初期濃度：５０ｐｐｍ
評価系：閉鎖循環式
反応器体積：２．８Ｌ
循環速度：３Ｌ／ｍｉｎ
光源・照度：ブラックライト１ｍＷ／ｃｍ２
照射面積：５×７ｃｍ２
暗吸着：３０ｍｉｎ
光照射：６０ｍｉｎ
(5) Evaluation of coating photocatalytic activity Using the above-mentioned photocatalyst, photocatalytic activity was evaluated in the coating. The evaluation was performed under the following conditions.
Reaction conditions Reaction gas: Acetaldehyde Initial concentration: 50 ppm
Evaluation system: closed circulation reactor volume: 2.8L
Circulation speed: 3L / min
Light source / illuminance: Black light 1 mW / cm 2
Irradiation area: 5 × 7 cm 2
Dark adsorption: 30 min
Light irradiation: 60 min
図１０に、本発明に係るｐ−Ｓｉ／／ＴｉＯ２とＳＴ−４１を用いた場合のアセトアルデヒド濃度と時間との関係を示している。図１０から分かるように、本発明に係るｐ−Ｓｉ／／ＴｉＯ２では、何も被覆していない光触媒（ＳＴ−４１）を用いた場合よりアセトアルデヒド濃度が減少した。また、反応速度定数を算出すると、本発明に係るｐ−Ｓｉ／／ＴｉＯ２では、反応速度定数は３．１８（／ｈｏｕｒ）であるのに対し、被覆のないＳＴ−４１では、２．４５（／ｈｏｕｒ）であり、１．３倍程度の反応速度を有することが分かった。 FIG. 10 shows the relationship between the acetaldehyde concentration and time when p-Si // TiO 2 and ST-41 according to the present invention are used. As can be seen from FIG. 10, in p-Si // TiO 2 according to the present invention, the concentration of acetaldehyde was reduced as compared with the case where a photocatalyst (ST-41) not coated with anything was used. When the reaction rate constant is calculated, the p-Si // TiO 2 according to the present invention has a reaction rate constant of 3.18 (/ hour), whereas ST-41 without coating has a value of 2.45. (/ Hour) and was found to have a reaction rate of about 1.3 times.
また、図１１に、従来例に係るｐ−Ｓｉ／ＴｉＯ２とＳＴ−４１を用いた場合のアセトアルデヒド濃度と時間との関係を示している。図１１から分かるように、従来例に係るｐ−Ｓｉ／ＴｉＯ２では、何も被覆していない光触媒（ＳＴ−４１）より、光触媒活性が劣ることが分かる。 FIG. 11 shows the relationship between the acetaldehyde concentration and time when p-Si / TiO 2 and ST-41 according to the conventional example are used. As can be seen from FIG. 11, the p-Si / TiO 2 according to the conventional example is inferior in the photocatalytic activity to the photocatalyst (ST-41) not coated with anything.
また、反応速度定数を算出すると、従来例に係るｐ−Ｓｉ／ＴｉＯ２では、反応速度定数は０．２１（／ｈｏｕｒ）であるのに対し、被覆のないＳＴ−４１では、２．５４（／ｈｏｕｒ）であり、ｐ−Ｓｉ／ＴｉＯ２を用いた場合の反応速度は、被覆のない光触媒（ＳＴ−４１）を用いた場合の反応速度の１０分の１程度であることが分かった。 When the reaction rate constant is calculated, the p-Si / TiO 2 according to the conventional example has a reaction rate constant of 0.21 (/ hour), whereas ST-41 without a coating has 2.54 ( It was found that the reaction rate when p-Si / TiO 2 was used was about 1/10 of the reaction rate when a photocatalyst without coating (ST-41) was used.
したがって、直接ポーラスシリカ層で光触媒粒子を被覆したものを塗膜に混合して使用した場合、光触媒の活性が著しく低下することが分かった。 Therefore, it was found that the activity of the photocatalyst was remarkably lowered when the porous silica layer coated with the photocatalyst particles was mixed with the coating film.
ＴＥＯＳ及びＯＤＴＳを用いた光触媒の作製
まず、石原産業株式会社製の光触媒用酸化チタン（ＴｉＯ２:ＳＴ-４１）を０．５Ｍグルコース水溶液に懸濁させ、これを１８０℃で６時間水熱処理して、炭素被覆ＴｉＯ２（以下、ｃ／ＴｉＯ２）を調製した。その後、このｃ／ＴｉＯ２をメタノール１０ｍｌの溶媒に分散させ、さらにこの溶液にアミノエチルアミノプロピルトリエトキシシラン（ＡＥＡＰ）を０．１ｍｌ加え２時間攪拌し、ＡＥＡＰ／ｃ／ＴｉＯ２を得た。２時間後、当該溶液に対して遠心分離を行い、ＡＥＡＰ／ｃ／ＴｉＯ２を回収した。その後、回収したＡＥＡＰ／ｃ／ＴｉＯ２を２０ｍｌの混合溶液（アセトニトリル：エタノール＝１：３）に分散させ、さらに、ＴＥＯＳ：ＯＤＴＳ（１：１、１：３、３：１）を１．０ｍｌ、アンモニア０．５ｍｌをさらに加え３６時間振とうした。加水分解・脱水縮合反応後、遠心分離を行った。回収したサンプルをエタノールで洗浄し遠心分離をして回収した。この作業を３回行い、その後乾燥させた。乾燥したサンプルを６００℃で２時間焼成し、ＯＤＴＳのオクタデシル基を除去し、これにより中空状ポーラスシリカ被覆ＴｉＯ２（ｐ−Ｓｉ／／ＴｉＯ２）を得た。窒素吸着測定から見積もられる得られたｐ−Ｓｉ／／ＴｉＯ２のＢＥＴ比表面積は、４０６．０ｍ２／ｇであった。また、窒素吸着等温線からミクロ細孔のサイズ分布を算出する解析法であるＳＦ法に基づいて、細孔サイズ分布をプロットすると、ｐ−Ｓｉ／／ＴｉＯ２は０．８ｎｍを中心とする発達したミクロ細孔をもつことが確認された。
Preparation of photocatalyst using TEOS and ODTS First, titanium oxide for photocatalyst (TiO 2 : ST-41) manufactured by Ishihara Sangyo Co., Ltd. was suspended in 0.5M glucose aqueous solution and hydrothermally treated at 180 ° C. for 6 hours. Thus, carbon-coated TiO 2 (hereinafter referred to as c / TiO 2 ) was prepared. Thereafter, this c / TiO 2 was dispersed in 10 ml of methanol, and 0.1 ml of aminoethylaminopropyltriethoxysilane (AEAP) was further added to this solution, followed by stirring for 2 hours to obtain AEAP / c / TiO 2 . After 2 hours, the solution was centrifuged to recover AEAP / c / TiO 2 . Thereafter, the recovered AEAP / c / TiO 2 was dispersed in 20 ml of a mixed solution (acetonitrile: ethanol = 1: 3), and 1.0 ml of TEOS: ODTS (1: 1, 3: 3, 3: 1) was further dispersed. Further, 0.5 ml of ammonia was added and shaken for 36 hours. Centrifugation was performed after the hydrolysis / dehydration condensation reaction. The collected sample was washed with ethanol and centrifuged to collect it. This operation was performed three times and then dried. The dried sample was baked at 600 ° C. for 2 hours to remove the octadecyl group of ODTS, thereby obtaining hollow porous silica-coated TiO 2 (p-Si // TiO 2 ). The BET specific surface area of the obtained p-Si // TiO 2 estimated from the nitrogen adsorption measurement was 406.0 m 2 / g. In addition, when the pore size distribution is plotted based on the SF method, which is an analysis method for calculating the micropore size distribution from the nitrogen adsorption isotherm, p-Si // TiO 2 develops around 0.8 nm. It was confirmed to have micropores.
本発明に係る光触媒は、特に、バインダーの劣化を起こさず長期間分解機能を維持する必要がある、家屋の壁面等に塗布する防汚剤として非常に有用である。また、塗料、塗膜、紙、繊維、プラスチックに混合して使用することもできる。 The photocatalyst according to the present invention is particularly useful as an antifouling agent applied to a wall surface of a house and the like that needs to maintain a decomposition function for a long time without causing deterioration of the binder. Moreover, it can also be used, mixing with a coating material, a coating film, paper, a fiber, and a plastic.
１ コア部
２ 中空層
２' 炭素含有層
３ 細孔形成剤からなる層
４ 多孔質シェル層
６ ミセル
７ 細孔
DESCRIPTION OF SYMBOLS 1 Core part 2 Hollow layer 2 'Carbon containing layer 3 Layer which consists of pore forming agents 4 Porous shell layer 6 Micellar 7 Pore
Claims (32)
前記コア部から離間して前記コア部を覆う多孔質シェル層と、を含み、
前記コア部と前記多孔質シェル層との間には中空層が設けられてなる光触媒であって、
窒素吸着法によって測定される、０．４〜５０ｎｍの範囲の細孔径の、単位重量当たりの細孔容積が０．１ｃｍ３／ｇ以上である光触媒。 A core containing photocatalytic particles;
A porous shell layer that covers the core portion apart from the core portion, and
A photocatalyst comprising a hollow layer provided between the core portion and the porous shell layer,
A photocatalyst having a pore diameter in the range of 0.4 to 50 nm and a pore volume per unit weight of 0.1 cm 3 / g or more as measured by a nitrogen adsorption method.
前記コア部の表面の少なくとも一部に直接炭素含有層を形成する第一工程と、
前記炭素含有層が形成されたコア部を懸濁させた溶媒に、細孔形成剤を混合して、前記炭素含有層を細孔形成剤で被覆するとともに、当該溶媒中に細孔形成剤を分散させる第二工程と、
前記溶媒中に多孔質シェル層の前駆物質を混合して、前記の炭素含有層表面を被覆する細孔形成剤の層上に、前記溶媒中に分散された細孔形成剤を含んでなる多孔質シェル層となる層を形成する第三工程と、
前記コア部と前記多孔質シェル層となる層との間にある前記炭素含有層及び前記細孔形成剤並びに前記多孔質シェル層となる層の壁内に含まれる細孔形成剤を除去する第四工程と、を含むことを特徴とする光触媒の作製方法。 A method for producing a photocatalyst comprising a core part containing photocatalyst particles and a porous shell layer covering the core part away from the core part,
A first step of directly forming a carbon-containing layer on at least a part of the surface of the core part;
A pore-forming agent is mixed in a solvent in which the core portion on which the carbon-containing layer is formed is suspended, and the carbon-containing layer is coated with the pore-forming agent, and the pore-forming agent is added to the solvent. A second step of dispersing;
A porous material comprising a pore-forming agent dispersed in the solvent on a layer of a pore-forming agent mixed with the precursor of the porous shell layer in the solvent and covering the surface of the carbon-containing layer. A third step of forming a layer to become a porous shell layer;
Removing the carbon-containing layer and the pore-forming agent between the core portion and the layer to be the porous shell layer, and the pore-forming agent contained in the walls of the layer to be the porous shell layer; A process for producing a photocatalyst comprising four steps.
前記コア部の表面の少なくとも一部に直接炭素含有層を形成する第一工程と、
前記炭素含有層が形成されたコア部を懸濁させた溶媒に、表面処理剤を混合して、前記炭素含有層の表面を当該表面処理剤で被覆する第二工程と、
前記溶媒中に細孔形成剤及び多孔質シェル層の前駆物質を混合して、前記表面処理剤の層上に、細孔形成剤を含んでなる多孔質シェル層となる層を形成する第三工程と、
前記コア部と前記多孔質シェル層となる層との間にある前記炭素含有層及び前記表面処理剤の層並びに前記多孔質シェル層となる層の壁内に含まれる細孔形成剤の一部を除去する第四工程と、を含むことを特徴とする光触媒の作製方法。 A method for producing a photocatalyst comprising a core part containing photocatalyst particles and a porous shell layer covering the core part away from the core part,
A first step of directly forming a carbon-containing layer on at least a part of the surface of the core part;
A second step of mixing a surface treatment agent in a solvent in which the core portion on which the carbon-containing layer is formed is suspended, and coating the surface of the carbon-containing layer with the surface treatment agent;
Third, a pore forming agent and a precursor of a porous shell layer are mixed in the solvent to form a layer that becomes a porous shell layer containing the pore forming agent on the surface treatment agent layer. Process,
Part of the pore-forming agent contained in the wall of the carbon-containing layer and the surface treatment agent layer between the core portion and the layer to be the porous shell layer, and the layer to be the porous shell layer And a fourth step of removing the photocatalyst.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2007128851A JP2008284411A (en) | 2007-05-15 | 2007-05-15 | Photocatalyst included in hollow porous shell layer and its manufacturing method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2007128851A JP2008284411A (en) | 2007-05-15 | 2007-05-15 | Photocatalyst included in hollow porous shell layer and its manufacturing method |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JP2008284411A true JP2008284411A (en) | 2008-11-27 |
Family
ID=40144648
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2007128851A Pending JP2008284411A (en) | 2007-05-15 | 2007-05-15 | Photocatalyst included in hollow porous shell layer and its manufacturing method |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2008284411A (en) |
Cited By (31)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2010065250A (en) * | 2008-09-09 | 2010-03-25 | Hiroshima Univ | Method for producing composite body, and composite body |
| JP2011020033A (en) * | 2009-07-14 | 2011-02-03 | Ishihara Sangyo Kaisha Ltd | Visible light-responsive photocatalyst, method for producing the same and photocatalyst coating agent and photocatalyst dispersion obtained by using the same |
| EP2295491A1 (en) * | 2009-09-14 | 2011-03-16 | Fujifilm Corporation | Protective film and front sheet for solar cell |
| JP2012125760A (en) * | 2010-12-10 | 2012-07-05 | Samsung Electronics Co Ltd | Adsorption cell, and method of manufacturing the same |
| CN102773085A (en) * | 2012-06-27 | 2012-11-14 | 天津大学 | Facilitated transport type TiO2/void/SiO2 photocatalysis particle and preparation method thereof |
| JP5087184B2 (en) * | 2010-08-06 | 2012-11-28 | Ｄｉｃ株式会社 | One-pack type coating composition, photocatalyst used therefor, coating film thereof, and production method thereof |
| KR101208918B1 (en) * | 2010-02-26 | 2012-12-06 | 한국조폐공사 | Magnetic Particle and the Fabrication Method Thereof |
| CN103071493A (en) * | 2013-01-11 | 2013-05-01 | 河海大学 | Preparation method of hollow Ag/Zno microsphere photocatalyst |
| JP2013521122A (en) * | 2010-03-10 | 2013-06-10 | ビーエーエスエフ ソシエタス・ヨーロピア | Process for producing mineral oils using a cationic surfactant having a hydrophobic block with a chain length of 6 to 10 carbon atoms |
| KR101339099B1 (en) | 2010-12-30 | 2013-12-10 | 한국조폐공사 | Magnetic Particle and the Fabrication Method Thereof |
| KR101339080B1 (en) | 2010-12-30 | 2013-12-10 | 한국조폐공사 | Magnetic Particle and the Fabrication Method Thereof |
| KR101339070B1 (en) | 2010-12-30 | 2013-12-10 | 한국조폐공사 | Magnetic Particle and the Fabrication Method Thereof |
| US20130330839A1 (en) * | 2010-11-24 | 2013-12-12 | Snu R&Db Foundation | Single nanoparticle having a nanogap between a core material and a shell material, and preparation method thereof |
| CN103586044A (en) * | 2013-11-29 | 2014-02-19 | 辽宁大学 | Double layer core-shell structure Ni-WO3 photocatalyst and application |
| JP2015505721A (en) * | 2011-12-01 | 2015-02-26 | ベーウェールＢｅｅｗａｉｒ | Method for treating effluents in a bed of microbeads by cold plasma and photocatalysis |
| KR101567388B1 (en) * | 2013-07-02 | 2015-11-10 | 한국과학기술연구원 | Metal oxides composite including hollow core and porous shell layer and the fabrication method thereof |
| CN105312038A (en) * | 2014-07-29 | 2016-02-10 | 中国科学院大连化学物理研究所 | Formylphenylboronic acid modified magnetic nanoparticles and preparation and application thereof |
| KR101611041B1 (en) | 2014-06-02 | 2016-04-08 | 성균관대학교산학협력단 | Organic network structure and method for manufacturing the same |
| CN105869897A (en) * | 2016-06-29 | 2016-08-17 | 扬州大学 | Preparation method and application of hollow material CeO2@TiO2 |
| US9776173B2 (en) | 2013-06-07 | 2017-10-03 | Lg Chem, Ltd. | Hollow metal nanoparticles |
| JP2018184322A (en) * | 2017-04-26 | 2018-11-22 | 富士ゼロックス株式会社 | Titanium oxide particle and method for producing the same, photocatalyst forming composition, photocatalyst, and structure |
| JP2018184321A (en) * | 2017-04-26 | 2018-11-22 | 富士ゼロックス株式会社 | Metatitanic acid particle and method for producing the same, photocatalyst forming composition, photocatalyst, and structure |
| CN110354844A (en) * | 2013-08-22 | 2019-10-22 | 夏普株式会社 | Photocatalyst material |
| CN113398971A (en) * | 2021-06-15 | 2021-09-17 | 华东理工大学 | Two-dimensional RuNi/g-C3N4Composite photocatalyst and preparation method and application thereof |
| CN113717589A (en) * | 2021-09-09 | 2021-11-30 | 徐州特之达包装科技有限公司 | Waterproof self-cleaning fiber coating and preparation method thereof |
| CN114042449A (en) * | 2021-11-28 | 2022-02-15 | 胡晨鸣 | Sulfur dioxide poisoning resistant catalyst for treating waste gas containing nitrogen oxide, waste gas treating agent and application of catalyst and waste gas treating agent |
| CN114191981A (en) * | 2021-12-26 | 2022-03-18 | 胡晨鸣 | Harmless treatment method for industrial waste gas |
| CN115945185A (en) * | 2022-09-28 | 2023-04-11 | 上海应用技术大学 | Preparation of full-spectrum-absorption photocatalytic spraying liquid and application of full-spectrum-absorption photocatalytic spraying liquid in lamp |
| CN116273022A (en) * | 2023-03-21 | 2023-06-23 | 昆明理工大学 | Catalytic material with hollow core-shell structure and preparation method and application thereof |
| CN116282159A (en) * | 2023-03-06 | 2023-06-23 | 河北工业大学 | Mesoporous Nb with large aperture 2 O 5 Photocatalytic material, preparation method and application thereof |
| CN118079910A (en) * | 2024-04-09 | 2024-05-28 | 临沂大学 | KNbO ₃/Ag@WO ₃ composite photocatalyst and preparation method and application thereof |
-
2007
- 2007-05-15 JP JP2007128851A patent/JP2008284411A/en active Pending
Cited By (39)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2010065250A (en) * | 2008-09-09 | 2010-03-25 | Hiroshima Univ | Method for producing composite body, and composite body |
| JP2011020033A (en) * | 2009-07-14 | 2011-02-03 | Ishihara Sangyo Kaisha Ltd | Visible light-responsive photocatalyst, method for producing the same and photocatalyst coating agent and photocatalyst dispersion obtained by using the same |
| EP2295491A1 (en) * | 2009-09-14 | 2011-03-16 | Fujifilm Corporation | Protective film and front sheet for solar cell |
| JP2011056907A (en) * | 2009-09-14 | 2011-03-24 | Fujifilm Corp | Protective film and front sheet for solar cell |
| KR101208918B1 (en) * | 2010-02-26 | 2012-12-06 | 한국조폐공사 | Magnetic Particle and the Fabrication Method Thereof |
| JP2013521122A (en) * | 2010-03-10 | 2013-06-10 | ビーエーエスエフ ソシエタス・ヨーロピア | Process for producing mineral oils using a cationic surfactant having a hydrophobic block with a chain length of 6 to 10 carbon atoms |
| JP5087184B2 (en) * | 2010-08-06 | 2012-11-28 | Ｄｉｃ株式会社 | One-pack type coating composition, photocatalyst used therefor, coating film thereof, and production method thereof |
| US9482618B2 (en) * | 2010-11-24 | 2016-11-01 | Korea Research Institute Of Chemical Technology | Single nanoparticle having a nanogap between a core material and a shell material, and preparation method thereof |
| US20130330839A1 (en) * | 2010-11-24 | 2013-12-12 | Snu R&Db Foundation | Single nanoparticle having a nanogap between a core material and a shell material, and preparation method thereof |
| JP2012125760A (en) * | 2010-12-10 | 2012-07-05 | Samsung Electronics Co Ltd | Adsorption cell, and method of manufacturing the same |
| KR101339099B1 (en) | 2010-12-30 | 2013-12-10 | 한국조폐공사 | Magnetic Particle and the Fabrication Method Thereof |
| KR101339080B1 (en) | 2010-12-30 | 2013-12-10 | 한국조폐공사 | Magnetic Particle and the Fabrication Method Thereof |
| KR101339070B1 (en) | 2010-12-30 | 2013-12-10 | 한국조폐공사 | Magnetic Particle and the Fabrication Method Thereof |
| JP2015505721A (en) * | 2011-12-01 | 2015-02-26 | ベーウェールＢｅｅｗａｉｒ | Method for treating effluents in a bed of microbeads by cold plasma and photocatalysis |
| CN102773085A (en) * | 2012-06-27 | 2012-11-14 | 天津大学 | Facilitated transport type TiO2/void/SiO2 photocatalysis particle and preparation method thereof |
| CN102773085B (en) * | 2012-06-27 | 2014-04-16 | 天津大学 | Facilitated transport type TiO2/void/SiO2 photocatalysis particle and preparation method thereof |
| CN103071493A (en) * | 2013-01-11 | 2013-05-01 | 河海大学 | Preparation method of hollow Ag/Zno microsphere photocatalyst |
| KR101858304B1 (en) * | 2013-06-07 | 2018-05-16 | 주식회사 엘지화학 | Hollow metal nano particles |
| US9776173B2 (en) | 2013-06-07 | 2017-10-03 | Lg Chem, Ltd. | Hollow metal nanoparticles |
| KR101567388B1 (en) * | 2013-07-02 | 2015-11-10 | 한국과학기술연구원 | Metal oxides composite including hollow core and porous shell layer and the fabrication method thereof |
| CN110354844A (en) * | 2013-08-22 | 2019-10-22 | 夏普株式会社 | Photocatalyst material |
| CN103586044A (en) * | 2013-11-29 | 2014-02-19 | 辽宁大学 | Double layer core-shell structure Ni-WO3 photocatalyst and application |
| KR101611041B1 (en) | 2014-06-02 | 2016-04-08 | 성균관대학교산학협력단 | Organic network structure and method for manufacturing the same |
| CN105312038A (en) * | 2014-07-29 | 2016-02-10 | 中国科学院大连化学物理研究所 | Formylphenylboronic acid modified magnetic nanoparticles and preparation and application thereof |
| CN105869897A (en) * | 2016-06-29 | 2016-08-17 | 扬州大学 | Preparation method and application of hollow material CeO2@TiO2 |
| CN105869897B (en) * | 2016-06-29 | 2017-12-08 | 扬州大学 | A kind of hollow material CeO2@TiO2Preparation method and applications |
| JP2018184322A (en) * | 2017-04-26 | 2018-11-22 | 富士ゼロックス株式会社 | Titanium oxide particle and method for producing the same, photocatalyst forming composition, photocatalyst, and structure |
| JP2018184321A (en) * | 2017-04-26 | 2018-11-22 | 富士ゼロックス株式会社 | Metatitanic acid particle and method for producing the same, photocatalyst forming composition, photocatalyst, and structure |
| CN113398971A (en) * | 2021-06-15 | 2021-09-17 | 华东理工大学 | Two-dimensional RuNi/g-C3N4Composite photocatalyst and preparation method and application thereof |
| CN113717589A (en) * | 2021-09-09 | 2021-11-30 | 徐州特之达包装科技有限公司 | Waterproof self-cleaning fiber coating and preparation method thereof |
| CN114042449A (en) * | 2021-11-28 | 2022-02-15 | 胡晨鸣 | Sulfur dioxide poisoning resistant catalyst for treating waste gas containing nitrogen oxide, waste gas treating agent and application of catalyst and waste gas treating agent |
| CN114042449B (en) * | 2021-11-28 | 2024-03-08 | 陕西省双菱化工股份有限公司 | Sulfur dioxide poisoning resistant catalyst for treating nitrogen oxide-containing waste gas, waste gas treating agent and application thereof |
| CN114191981A (en) * | 2021-12-26 | 2022-03-18 | 胡晨鸣 | Harmless treatment method for industrial waste gas |
| CN114191981B (en) * | 2021-12-26 | 2024-03-22 | 中环科力(北京)环境科技发展中心 | Harmless treatment method for industrial waste gas |
| CN115945185A (en) * | 2022-09-28 | 2023-04-11 | 上海应用技术大学 | Preparation of full-spectrum-absorption photocatalytic spraying liquid and application of full-spectrum-absorption photocatalytic spraying liquid in lamp |
| CN116282159A (en) * | 2023-03-06 | 2023-06-23 | 河北工业大学 | Mesoporous Nb with large aperture 2 O 5 Photocatalytic material, preparation method and application thereof |
| CN116273022A (en) * | 2023-03-21 | 2023-06-23 | 昆明理工大学 | Catalytic material with hollow core-shell structure and preparation method and application thereof |
| CN116273022B (en) * | 2023-03-21 | 2024-06-07 | 昆明理工大学 | Catalytic material with hollow core-shell structure and preparation method and application thereof |
| CN118079910A (en) * | 2024-04-09 | 2024-05-28 | 临沂大学 | KNbO ₃/Ag@WO ₃ composite photocatalyst and preparation method and application thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP2008284411A (en) | Photocatalyst included in hollow porous shell layer and its manufacturing method | |
| JP6753781B2 (en) | Titania particles and their manufacturing method | |
| KR101323303B1 (en) | Porous composite compound, manufacturing method thereof and cement composition containing porous composite compound | |
| JP5499442B2 (en) | Metal oxide encapsulated mesoporous silica capsule | |
| TWI324948B (en) | Photocatalystic composite material, method for producing the same and application thereof | |
| WO2007023558A1 (en) | Tungsten oxide photocatalyst, process for producing the same, and fiber cloth having deodorizing/antifouling function | |
| JP2002285691A (en) | Interior material | |
| JP4319184B2 (en) | PHOTOCATALYST, ITS MANUFACTURING METHOD, AND ARTICLE USING PHOTOCATALYST | |
| JP2008127405A (en) | Core-shell type spherical silica-based mesoporous body and catalyst and adsorbent using the same | |
| Racles et al. | A silica-silver nanocomposite obtained by sol-gel method in the presence of silver nanoparticles | |
| Chen et al. | Template-free sol–gel preparation and characterization of free-standing visible light responsive C, N-modified porous monolithic TiO2 | |
| KR101467836B1 (en) | Paint composition containing porous composite compound | |
| JP2002138376A (en) | Interior material | |
| JP2002045650A (en) | Moisture-controllable, photocatalyst interior wall material, method for producing the same and coating composition for moisture-controllable, photocatalyst interior wall material | |
| JP4540971B2 (en) | Neutral titanium oxide sol and method for producing the same | |
| JP4163374B2 (en) | Photocatalytic membrane | |
| JP5358433B2 (en) | Composite, method for producing the same, and composition containing the same | |
| JP5090787B2 (en) | Titanium oxide composite particle aqueous dispersion and production method thereof | |
| JP2010150434A (en) | Method for manufacturing weatherproof and foulingproof emulsion coating material and coated film thereof | |
| KR101677842B1 (en) | Multifunctional Cu-TiO2-PU having both photocatalyst and adsorbent activity and manufacturing method thereof | |
| JP3978636B2 (en) | Coating composition for photocatalyst film formation | |
| JPH105598A (en) | Photocatalyst powder, photocatalyst body using the same and their production, and environmental cleaning method using them | |
| JP4522082B2 (en) | Photocatalyst liquid composition and photocatalyst formed using the same | |
| JP2001096154A (en) | Vanadium oxide/titania hybrid photocatalyst and its manufacturing method | |
| CN105457635A (en) | Photocatalytic filter for degrading mixed gas and manufacturing method thereof |