CN101033343A - Photocatalyst dispersoid - Google Patents
Photocatalyst dispersoid Download PDFInfo
- Publication number
- CN101033343A CN101033343A CNA200710092400XA CN200710092400A CN101033343A CN 101033343 A CN101033343 A CN 101033343A CN A200710092400X A CNA200710092400X A CN A200710092400XA CN 200710092400 A CN200710092400 A CN 200710092400A CN 101033343 A CN101033343 A CN 101033343A
- Authority
- CN
- China
- Prior art keywords
- photocatalyst
- dispersoid
- ammonium phosphate
- silicon compound
- polymerizability
- 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 144
- 150000003377 silicon compounds Chemical class 0.000 claims abstract description 49
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 30
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000002904 solvent Substances 0.000 claims abstract description 10
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical group O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 38
- 230000001699 photocatalysis Effects 0.000 claims description 32
- ZRIUUUJAJJNDSS-UHFFFAOYSA-N ammonium phosphates Chemical compound [NH4+].[NH4+].[NH4+].[O-]P([O-])([O-])=O ZRIUUUJAJJNDSS-UHFFFAOYSA-N 0.000 claims description 25
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 25
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 claims description 6
- 239000006185 dispersion Substances 0.000 abstract description 40
- 239000004254 Ammonium phosphate Substances 0.000 abstract description 8
- 229910000148 ammonium phosphate Inorganic materials 0.000 abstract description 8
- 235000019289 ammonium phosphates Nutrition 0.000 abstract description 8
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 description 34
- 239000007787 solid Substances 0.000 description 24
- 239000000463 material Substances 0.000 description 22
- 239000000843 powder Substances 0.000 description 16
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 15
- 238000000354 decomposition reaction Methods 0.000 description 15
- 238000000034 method Methods 0.000 description 14
- 238000006243 chemical reaction Methods 0.000 description 13
- 230000000052 comparative effect Effects 0.000 description 11
- 239000000126 substance Substances 0.000 description 11
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 10
- 238000013459 approach Methods 0.000 description 10
- 150000002500 ions Chemical group 0.000 description 10
- 238000002156 mixing Methods 0.000 description 10
- 230000007935 neutral effect Effects 0.000 description 10
- 239000003513 alkali Substances 0.000 description 9
- 238000007146 photocatalysis Methods 0.000 description 9
- 238000010790 dilution Methods 0.000 description 8
- 239000012895 dilution Substances 0.000 description 8
- 150000003609 titanium compounds Chemical class 0.000 description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 239000002585 base Substances 0.000 description 6
- 239000002612 dispersion medium Substances 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 230000006641 stabilisation Effects 0.000 description 6
- 238000011105 stabilization Methods 0.000 description 6
- -1 amine compound Chemical class 0.000 description 5
- 229910021529 ammonia Inorganic materials 0.000 description 5
- 235000011114 ammonium hydroxide Nutrition 0.000 description 5
- 239000011248 coating agent Substances 0.000 description 5
- 238000000576 coating method Methods 0.000 description 5
- 239000000084 colloidal system Substances 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- 239000000377 silicon dioxide Substances 0.000 description 5
- 239000004408 titanium dioxide Substances 0.000 description 5
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 4
- 239000000654 additive Substances 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 238000005286 illumination Methods 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 229910017604 nitric acid Inorganic materials 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 239000010936 titanium Substances 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 3
- 238000013019 agitation Methods 0.000 description 3
- 239000011324 bead Substances 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 239000002609 medium Substances 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 239000003381 stabilizer Substances 0.000 description 3
- 229910052719 titanium Inorganic materials 0.000 description 3
- 229910000349 titanium oxysulfate Inorganic materials 0.000 description 3
- 241000186046 Actinomyces Species 0.000 description 2
- 241000894006 Bacteria Species 0.000 description 2
- 241000195493 Cryptophyta Species 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- 241000208125 Nicotiana Species 0.000 description 2
- 235000002637 Nicotiana tabacum Nutrition 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Chemical compound [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 description 2
- 230000033228 biological regulation Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229910052797 bismuth Inorganic materials 0.000 description 2
- 238000009395 breeding Methods 0.000 description 2
- 230000001488 breeding effect Effects 0.000 description 2
- 229910052793 cadmium Inorganic materials 0.000 description 2
- 238000005119 centrifugation Methods 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 239000012065 filter cake Substances 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000012467 final product Substances 0.000 description 2
- 239000000796 flavoring agent Substances 0.000 description 2
- 235000019634 flavors Nutrition 0.000 description 2
- 229910052733 gallium Inorganic materials 0.000 description 2
- 238000001879 gelation Methods 0.000 description 2
- 229910052732 germanium Inorganic materials 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 229910052735 hafnium Inorganic materials 0.000 description 2
- 229910052738 indium Inorganic materials 0.000 description 2
- 229910052741 iridium Inorganic materials 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 229910052746 lanthanum Inorganic materials 0.000 description 2
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum oxide Inorganic materials [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 description 2
- 229910052745 lead Inorganic materials 0.000 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 229910052750 molybdenum Inorganic materials 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 229910052758 niobium Inorganic materials 0.000 description 2
- 239000010955 niobium Substances 0.000 description 2
- 229910052762 osmium Inorganic materials 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 238000012856 packing Methods 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- 230000002093 peripheral effect Effects 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 238000004321 preservation Methods 0.000 description 2
- 230000005855 radiation Effects 0.000 description 2
- 229910052702 rhenium Inorganic materials 0.000 description 2
- 229910052703 rhodium Inorganic materials 0.000 description 2
- 229910052707 ruthenium Inorganic materials 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- IATRAKWUXMZMIY-UHFFFAOYSA-N strontium oxide Chemical compound [O-2].[Sr+2] IATRAKWUXMZMIY-UHFFFAOYSA-N 0.000 description 2
- 229910052715 tantalum Inorganic materials 0.000 description 2
- 229910052713 technetium Inorganic materials 0.000 description 2
- 229910052716 thallium Inorganic materials 0.000 description 2
- 229910052718 tin Inorganic materials 0.000 description 2
- LLZRNZOLAXHGLL-UHFFFAOYSA-J titanic acid Chemical compound O[Ti](O)(O)O LLZRNZOLAXHGLL-UHFFFAOYSA-J 0.000 description 2
- 229910052721 tungsten Inorganic materials 0.000 description 2
- 229910052720 vanadium Inorganic materials 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 229910052724 xenon Inorganic materials 0.000 description 2
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 229910052726 zirconium Inorganic materials 0.000 description 2
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 1
- HLLSOEKIMZEGFV-UHFFFAOYSA-N 4-(dibutylsulfamoyl)benzoic acid Chemical compound CCCCN(CCCC)S(=O)(=O)C1=CC=C(C(O)=O)C=C1 HLLSOEKIMZEGFV-UHFFFAOYSA-N 0.000 description 1
- 239000005995 Aluminium silicate Substances 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 1
- AVXURJPOCDRRFD-UHFFFAOYSA-N Hydroxylamine Chemical compound ON AVXURJPOCDRRFD-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 1
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical class CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- OLBVUFHMDRJKTK-UHFFFAOYSA-N [N].[O] Chemical compound [N].[O] OLBVUFHMDRJKTK-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical compound [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 229910000323 aluminium silicate Inorganic materials 0.000 description 1
- 229910021417 amorphous silicon Inorganic materials 0.000 description 1
- 230000003373 anti-fouling effect Effects 0.000 description 1
- 239000012736 aqueous medium Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000003115 biocidal effect Effects 0.000 description 1
- 229910000416 bismuth oxide Inorganic materials 0.000 description 1
- 230000001680 brushing effect Effects 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- 239000001506 calcium phosphate Substances 0.000 description 1
- 229910000389 calcium phosphate Inorganic materials 0.000 description 1
- 235000011010 calcium phosphates Nutrition 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 229910000420 cerium oxide Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000012885 constant function Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000000254 damaging effect Effects 0.000 description 1
- 238000010908 decantation Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000001877 deodorizing effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000003292 diminished effect Effects 0.000 description 1
- 238000003618 dip coating Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000001815 facial effect Effects 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 229910003437 indium oxide Inorganic materials 0.000 description 1
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 229940090044 injection Drugs 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 229910000765 intermetallic Inorganic materials 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 229910052754 neon Inorganic materials 0.000 description 1
- GKAOGPIIYCISHV-UHFFFAOYSA-N neon atom Chemical compound [Ne] GKAOGPIIYCISHV-UHFFFAOYSA-N 0.000 description 1
- 229910000480 nickel oxide Inorganic materials 0.000 description 1
- 229910000484 niobium oxide Inorganic materials 0.000 description 1
- 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 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 description 1
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 1
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 1
- UJMWVICAENGCRF-UHFFFAOYSA-N oxygen difluoride Chemical compound FOF UJMWVICAENGCRF-UHFFFAOYSA-N 0.000 description 1
- DCKVFVYPWDKYDN-UHFFFAOYSA-L oxygen(2-);titanium(4+);sulfate Chemical compound [O-2].[Ti+4].[O-]S([O-])(=O)=O DCKVFVYPWDKYDN-UHFFFAOYSA-L 0.000 description 1
- 238000010979 pH adjustment Methods 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 1
- 235000015320 potassium carbonate Nutrition 0.000 description 1
- 235000019353 potassium silicate Nutrition 0.000 description 1
- 238000011085 pressure filtration Methods 0.000 description 1
- 239000011164 primary particle Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000001603 reducing effect Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 235000017550 sodium carbonate Nutrition 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000011973 solid acid Substances 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- UUCCCPNEFXQJEL-UHFFFAOYSA-L strontium dihydroxide Chemical compound [OH-].[OH-].[Sr+2] UUCCCPNEFXQJEL-UHFFFAOYSA-L 0.000 description 1
- 229910001866 strontium hydroxide Inorganic materials 0.000 description 1
- XTQHKBHJIVJGKJ-UHFFFAOYSA-N sulfur monoxide Chemical compound S=O XTQHKBHJIVJGKJ-UHFFFAOYSA-N 0.000 description 1
- 229910000348 titanium sulfate Inorganic materials 0.000 description 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 description 1
- 229910001930 tungsten oxide Inorganic materials 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
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Abstract
The photocatalyst dispersion of the present invention is a dispersion having photocatalyst and water system solvent, wherein, an ammonium phosphate with a proportion lower than 5 weight portion relative to 100 weight portion of the photocatalyst is contained, and, a polymeric silicon compound is not contained or a polymeric silicon compound with a proportion lower than 7.5 weight portion relative to 100 weight portion of the photocatalyst dispersion is contained, and the value of the polymeric silicon compound/ammonium phosphate (weight proportion) is lower than 5, PH is 5-9.
Description
Technical field
The present invention relates to a kind of photocatalyst dispersoid of filming that manifests photocatalytic activity that is used to form.
Background technology
During to the semi-conductor irradiates light, generate electronics with strong reducing action and hole,, decompose the molecular species that contacts with semi-conductor by redoxomorphism with strong oxidation.Such effect is called photocatalysis,, can makes the decomposition such as organism in water and the atmosphere innoxious by utilizing this photocatalysis.Therefore, the material that manifests photocatalysis is a photocatalyst, begins in recent years to popularize in for example water treatment, deodorizing, off gas treatment, atmospheric cleaning, soil treatment, antibiotic anti-mildew, antifouling anti-various uses such as turbid.
As the material that manifests photocatalysis is photocatalyst, and for example titanium dioxide powder uses the most extensively, also practicability.
; actual when using photocatalyst such as titanium dioxide powder, the photocatalyst of titanium dioxide powder etc. and base material etc. need be fixed, as one of gimmick; be a kind of photocatalyst to be dispersed in the liquid medium, be coated in method on base material etc. with the state of dispersion.
The dispersion of photocatalyst roughly is divided into the dispersion of the pH that demonstrates acidic region, demonstrates the dispersion of the pH of neutral region, demonstrates the dispersion of the pH in alkalescence zone, uses according to differences such as purposes usually.For example, consider the corrodibility of base material and to the problem of the hazardness of human body the time etc., wish preferably not to be acid and alkalescence but to have the dispersion of neutral region pH.But, in neutral region, exist to be difficult to the such shortcoming of dispersed light catalyst particle, worry the dispersion stabilization variation, the result can not stably form coated film.
Therefore, in the past,, adopted to make it contain ammonium phosphate salt as the such way of dispersion stabilizer in order in the dispersion of the pH with neutral region, to guarantee good dispersion stabilization.
As the photocatalyst dispersoid that contains ammonium phosphate salt, proposition has and for example comprises photocatalyst, polymerizability silicon compound, ammonium phosphate and dispersion medium, the content of ammonium phosphate is in the coating material (USP6783845) that the oxide particle of coating (spy opens the 2005-54139 communique) in ammonium phosphate/polymerizability silicon compound=1/30～1/8 scope and combination phosphate cpd tackiness agent and median size 1～300nm forms by weight.
Summary of the invention
But, in photocatalyst dispersoid, too much add in ammonium phosphate salt or the polymerizability silicon compound, have the photocatalyst activity downward trend, the spy opens that disclosed dispersion also exists according to the inadequate situation of purposes photocatalyst activity among 2005-54139 communique and the USP6783845.Therefore, just require a kind of dispersion stabilization of not only having guaranteed neutral region, but also can form the photocatalyst dispersoid of the coated film of the high photocatalytic activity of performance.
Therefore, problem of the present invention is, a kind of photocatalyst dispersoid that just can easily form the coated film that shows high photocatalytic activity by visible light radiation in neutral region is provided.
The present inventor is in order to solve above-mentioned problem, and the result of research with keen determination repeatedly finds by making it contain an amount of ammonium phosphate salt as dispersion stabilizer, even also can form stable coated film at neutral region; Simultaneously, by making it not contain the polymerizability silicon compound that often contains as existing tackiness agent fully, even or contain also than existing content lack (with respect to photocatalyst and ammonium phosphate salt for the two for a small amount of), can solve above-mentioned problem at one stroke, and finally finish the present invention.
That is, the present invention relates to following formation.
(1) a kind of photocatalyst dispersoid, it is the dispersion that comprises photocatalyst and water solvent, it is characterized in that, in containing ammonium phosphate salt less than the ratio of 5 weight parts with respect to photocatalyst 100 weight parts, and do not contain the polymerizability silicon compound or contain the polymerizability silicon compound in the ratio below 7.5 weight parts with respect to photocatalyst 100 weight parts, the value of polymerizability silicon compound/ammonium phosphate salt (weight ratio) is below 5 simultaneously, and pH is 5～9.
(2) photocatalyst dispersoid of above-mentioned (1), photocatalyst is a titanium oxide.
(3) above-mentioned (1) or (2) described photocatalyst dispersoid, photocatalyst shows photocatalytic activity to the rayed of luminescent lamp.
(4) any described photocatalyst dispersoid in above-mentioned (1)～(3), ammonium phosphate salt is any one party or two sides of primary ammonium phosphate and Secondary ammonium phosphate.
According to photocatalyst dispersoid of the present invention, have and so-calledly can in neutral region, easily form the effect that shows the coated film of high photocatalytic activity by radiation of visible light.That is, photocatalyst dispersoid of the present invention to photocatalysis body such as various material coating such as for example filamentary material, material of construction, automotive material etc., can be given high photocatalytic activity to these materials easily.Be endowed the various materials of photocatalytic activity by photocatalyst dispersoid of the present invention, can decompose the NOx in the atmosphere, the breeding of repugnant substance (for example, tobacco flavor) in decomposition living space and the working space, inhibition bacterium (for example actinomyces), algae, mould etc.
Embodiment
Photocatalyst dispersoid of the present invention comprises photocatalyst and water solvent.
Photocatalyst of the present invention can be the powder that contains the composition that manifests photocatalytic activity, for example, can list the powder of the oxide compound more than a kind or 2 kinds that composition is the such metallic element of Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W, Mn, Tc, Re, Fe, Co, Ni, Ru, Rh, Pd, Os, Ir, Pt, Cu, Ag, Au, Zn, Cd, Ga, In, Tl, Ge, Sn, Pb, Bi, La, Ce, nitride, sulfide, oxynitride, oxysulfide, nitrogen fluorochemical, oxygen fluoride, oxygen nitrogen fluorochemical etc.Among these powder, preferred especially titanium oxide is as photocatalyst of the present invention.In more detail, titanium oxide has Detitanium-ore-type and rutile-type, based on preferred anatase-type titanium oxide on this aspect of photocatalytic activity.Under the situation of anatase-type titanium oxide, preferably its anatase octahedrite rate is more than 40%, more preferably more than 60%, most preferably more than 80%.Have again, measure grating spectrum, obtain the peak area of the strongest interference line (facial index 101) that is in the titanium oxide in this spectrum, just can calculate the anatase octahedrite rate of this moment by utilizing X-ray diffraction method.
As the titanium oxide of photocatalyst use, for example, by making titanium compound and alkali reaction, in resultant, add ammonia, after slaking, carry out solid-liquid separation, then, method of roasting solid substance (the following this method that also claims is " titanium oxide modulator approach A ") etc. just can modulate out.Below, this titanium oxide modulator approach A is described, but much less, the photocatalyst among the present invention is not limited to obtain by this modulator approach.
In titanium oxide modulator approach A,, for example can use titanous chloride [TiCl as titanium compound
3], titanium tetrachloride [TiCl
4], titanium sulfate [Ti (SO
4)
2MH
2O, 0≤m≤20], titanyl sulfate [TiOSO
4NH
2O, 0≤n≤20], chlorination oxygen titanium [TiOCl
2] etc., as with the alkali of titanium compound reaction, for example, can use sodium hydroxide, potassium hydroxide, yellow soda ash, salt of wormwood, ammonia, hydrazine, azanol, monoethanolamine, non-ring type amine compound, ring type fatty amine compound etc.
In titanium oxide modulator approach A, the reaction of titanium compound and alkali be pH2 above, preferably more than pH3, below the pH7, carry out best in the following scope of preferred pH5.The temperature of reaction of titanium compound and alkali is generally below 90 ℃, preferably below 70 ℃, more preferably below 55 ℃.In addition, the reaction of titanium compound and alkali can be carried out existing under the situation of aqueous hydrogen peroxide solution.
In titanium oxide modulator approach A, to by when resultant that titanium compound and alkali reaction obtained adds the ammonia slaking, preferably the amount of the ammonia that adds is set at and the total amount of the amount of employed alkali is surpassed under the situation that has water make titanium compound become the stoichiometry of the necessary alkali of titanium hydroxide.Particularly, preferred above-mentioned stoichiometry is more than 1.1 times of benchmark, more preferably more than 1.5 times.Have again,,, can not obtain the effect that matches with this amount even if the amount of alkali is more for the upper limit of this moment, just unfavorable in economic aspect, so preferred above-mentioned stoichiometry is below 20 times of benchmark, more preferably below 10 times.
In titanium oxide modulator approach A, the temperature when adding the ammonia slaking for example is more than 0 ℃, preferred more than 10 ℃, below 110 ℃, preferred below 80 ℃, more preferably below 55 ℃; The time of slaking is 1 minute～10 hours, preferred 10 minutes～2 hours, carries out while can stir the method that keeps.
In titanium oxide modulator approach A, the solid-liquid separation of the resultant after the slaking for example can be by pressure filtration, and filtration under diminished pressure, centrifugation, decantation wait and carry out.In addition, in the solid-liquid separation, preferably carry out according to the operation of washing the solid substance that is obtained.
In titanium oxide modulator approach A, can for example use devices such as air-flow stoving oven, continuous tunnel furnace, converter, with usually more than 300 ℃, preferably more than 350 ℃, below 600 ℃, preferably below 500 ℃, more preferably the temperature in the scope below 400 ℃ is carried out solid substance that solid-liquid separation goes out or the roasting of carrying out the solid substance of any washing.Roasting time can decide according to maturing temperature and calciner etc., cannot treat different things as the same, and is generally 10 minutes～30 hours, preferred 30 minutes～5 hours.
In titanium oxide modulator approach A, in the titanium oxide that roasting obtained, as required, also can the load tungsten oxide, niobium oxide, ferriferous oxide, the such compound that manifests solid acid of nickel oxide, or the compound of the such demonstration solid alkaline of lanthanum-oxides, cerium oxide, or the metallic compound of the such absorption visible light of indium oxide, bismuth oxide compound etc.
Preferred photocatalyst of the present invention is the photocatalyst that the rayed of luminescent lamp is shown photocatalytic activity.At length, preferably manifest the photocatalyst of photocatalytic activity with respect to the rayed of the about 430nm of wavelength～about 830nm.Particularly, pulverous photocatalyst and acetaldehyde are put into hermetically sealed container, after airtight, by being positioned at the light time of light source (for example 500W xenon lamp) the about 430nm of the illumination wavelength～about 830nm apart from the position of the about 15cm of photocatalyst, the average decomposition rate of 20 minutes (beginning after 20 minutes, to end) of preferred acetaldehyde from irradiation, per 1 gram photocatalyst is more than the 10 μ mol/h, more preferably more than the 20 μ mol/h.
The photocatalyst powder that exists in the photocatalyst dispersoid of the present invention, its average primary particle diameter is generally below the 500nm, is preferably below the 200nm, more preferably below the 180nm.In addition, its average aggregate particle size gets final product below being generally 15 μ m.
The shared content of photocatalyst is suitably set according to purposes in the photocatalyst dispersoid of the present invention, though limit especially, be limited to more than the 0.1 weight % under setting usually, more than the preferred 1 weight %, on be limited to below the 30 weight %.Have, the content of photocatalyst (being the amount of the powder in the dispersion) is many more again, just can carry out mixing described later (particularly the initial stage mixes) more effectively.
Consider these, preestablish the content of photocatalyst when feeding intake, make them more,, add solvent,, just can become desirable content through dilution in the back operation than specified amount.
Water solvent among the present invention is principal constituent with water, as long as can dissolve the aftermentioned ammonium phosphate salt, for example, can enumerate such aqueous medium of the mixed solvent of alcohols such as water outlet, ethanol, methyl alcohol, 2-propyl alcohol, butanols and water etc., in the middle of them, special preferably water.
Photocatalyst dispersoid of the present invention contains ammonium phosphate salt.By making it contain the ammonium phosphate salt that works as dispersion stabilizer, in dispersion, also keep the dispersion stabilization of photocatalyst powder fully as pH with neutral region, can form stable coat film.In addition, for example, carry out dispersion treatment of certain hour etc., obtain finer dispersion, can form the higher photocatalyst film of transparency by utilizing the wet type medium mill.
As above-mentioned ammonium phosphate salt,, preferably list any one or two kinds of primary ammonium phosphate and Secondary ammonium phosphate even on a small amount of this aspect that also obtains sufficient dispersion stabilization easily.Especially, preferably phosphoric acid ammonium dihydrogen.
Important part is, the content of above-mentioned ammonium phosphate salt is ratio less than 5 weight parts with respect to photocatalyst 100 weight parts.Ammonium phosphate salt has this advantage of dispersion stabilization of the photocatalyst powder in the aforesaid raising dispersion, and the content of ammonium phosphate salt is many more, and this advantage is just obvious more.But, on the other hand, the content of ammonium phosphate salt for a long time (particularly, with respect to photocatalyst 100 weight parts, be that 8 weight parts are when above), will produce that the photocatalytic activity that uses the coat film that dispersion obtains descends, the viscosity of when long-time the preservation (particularly under the atmosphere of high temperature (particularly about 40 ℃)) dispersion such problem that can rise in the preservation process.
Photocatalyst dispersoid of the present invention does not contain the polymerizability silicon compound or to contain the polymerizability silicon compound with respect to photocatalyst 100 weight parts in the ratio below 7.5 weight parts.That is, do not contain the polymerizability silicon compound that contains mostly as existing tackiness agent fully, even or contain sometimes, also as above-mentioned scope, lack than existing content.
As above-mentioned polymerizability silicon compound, for example can list: the hydrolysis resultant of organoalkoxysilane, organoalkoxysilane, the partial condensate of organoalkoxysilane, water glass, colloid silica etc.It also can be more than 2 kinds that these polymerizability silicon compounds both can be independent a kind.
When photocatalyst dispersoid of the present invention comprised the polymerizability silicon compound, as mentioned above, its content was ratio below 7.5 weight parts with respect to photocatalyst 100 weight parts.Preferably, the content of polymerizability silicon compound less than 2 weight parts, is 0 weight part with respect to photocatalyst 100 weight parts with respect to photocatalyst 100 weight parts more preferably, does not promptly contain the polymerizability silicon compound.Because the content of polymerizability silicon compound for a long time, the photocatalytic activity downward trend of the photocatalyst coating film that is obtained is so make the content of polymerizability silicon compound few more good more as much as possible.
When photocatalyst dispersoid of the present invention contained the polymerizability silicon compound, based on the viewpoint that improves photocatalytic activity, also the value of preferred polymeric silicon compound/ammonium phosphate salt (weight ratio) was below 5.
Photocatalyst dispersoid of the present invention, pH are 5～9.More preferably pH is 6～8.Photocatalyst dispersoid of the present invention owing to have the pH of such neutral region, does not produce corrodibility and human body is not had dangerous such advantage various base materials so exist.
In photocatalyst dispersoid of the present invention, in the scope of not damaging effect of the present invention, can make as required and contain various additives in the photocatalyst dispersoid.As various additives, for example can list amorphous silicon di-oxide, the Si oxide that silicon sol is such, the non-crystalline state aluminum oxide, aluminum oxide that aluminium colloidal sol is such and oxyhydroxide, zeolite, the aluminosilicate that kaolin is such, magnesium oxide, calcium oxide, strontium oxide, barium oxide, magnesium hydroxide, calcium hydroxide, strontium hydroxide, the oxide compound of the alkaline-earth metal that hydrated barta is such and oxyhydroxide, calcium phosphate, molecular sieve, gac and Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W, Mn, Tc, Re, Fe, Co, Ni, Ru, Rh, Pd, Os, Ir, Pt, Cu, Ag, Au, Zn, Cd, Ga, In, Tl, Ge, Sn, Pb, Bi, La, the oxyhydroxide of the metallic element that Ce is such and the non-crystal oxide of these metallic elements etc.These additives both can be independent a kind, also can be more than 2 kinds.
Obtain photocatalyst dispersoid of the present invention, as long as mix for example above-mentioned photocatalyst, above-mentioned ammonium phosphate salt and above-mentioned water solvent, polymerizability silicon compound as required, further as required various additives.
In above-mentioned mixing, can use to make photocatalyst powder be distributed to device in the water solvent, for example, can adopt media-agitation type dispersion machine, roating sphere grinding machine, the such device of vibromill.Special recommendation working medium stirring-type dispersion machine in the middle of these.In addition, the dispersion medium as in these devices for example can use, and material is zirconium white, aluminum oxide or glass, below the diameter 0.65mm, and below the preferred 0.5mm, the more preferably following bead of 0.3mm etc.
Above-mentioned mixing also can be divided into more than 2 stages and carrying out, and for example, can use the device of the big relatively dispersion medium of diameter of packing into to carry out in the 1st stage, after the 2nd stage, uses the device of the dispersion medium that the diameter of packing into reduces successively to carry out.Like this,, photocatalyst powder is distributed in the water solvent, obtains the homodisperse dispersion of photocatalyst by carrying out multistage mixing.
Above-mentioned mixing is usually less than 40 ℃, preferred below 30 ℃, common more than 10 ℃, preferably carries out more than 20 ℃.When under exceeding the temperature of above-mentioned scope, mixing, worry dispersed can decline.
When obtaining photocatalyst dispersoid of the present invention, can also implement operations such as the removal of big particle, the adjustment of photocatalyst content (dilution etc.), pH adjustment to the mixture that obtains by above-mentioned mixing further as required.As the concrete grammar of these operations, do not limit especially, can adopt existing known method.
When preserving photocatalyst dispersoid of the present invention, preferably under the condition of irradiates light not, preserve, for example, preferably in the darkroom, preserve, or the transmitance of pack into ultraviolet ray and visible light is preserved in the opacifying property container below 10% respectively.
When using photocatalyst dispersoid of the present invention to form coat film, for example, can utilize existing known method such as spin coated, dip coating, scraper coating, spraying or brushing to apply dispersion, after this, heat etc. with the temperature that can remove the water solvent in the dispersion and to get final product.
Can carry out the coat film formation of photocatalyst dispersoid of the present invention to for example all base materials such as glass, plastics, metal, pottery, concrete.
Coat film (being photocatalysis body) by photocatalyst dispersoid of the present invention forms for example is performed as follows use.That is, list in seeing through the Glass Containers of visible light and putting into photocatalysis body and object being treated, use light source to the method for the visible light more than the photocatalysis body illumination wavelength 430nm etc.Irradiation time can suitably be selected according to the light intensity of light source and the kind and the amount of object being treated.As long as the light source that uses can the above visible light of illumination wavelength 430nm, just limit, and can use sunlight, luminescent lamp, halogen lamp, black lamp, xenon lamp, neon sign, LED, mercuryvapour lamp or sodium vapor lamp etc.
For example, photocatalyst dispersoid of the present invention forms photocatalysis body to various materials such as filamentary material, material of construction, automotive material easily, can give high photocatalytic activity to these materials.Be endowed the various materials of photocatalytic activity by photocatalyst dispersoid of the present invention, can decompose NOx in the atmosphere, decompose repugnant substance (for example, tobacco flavor) in living space and the working space, suppress the breedings of bacterium (for example actinomyces), algae, mould etc.
Embodiment
Hereinafter, will enumerate embodiment and comparative example describes the present invention in detail, the invention is not restricted to following examples.
Have again, carry out the measurement of the median size in embodiment and the comparative example and the evaluation of photocatalytic activity in order to following method.
The measurement of＜median size 〉
Use sub-micro granularity apparatus for measuring distribution (" N4Puls " that コ one Le one company makes), the median size of measure sample (nm).
The evaluation of＜photocatalytic activity (acetaldehyde decomposition ability) 〉
With the photocatalyst dispersoid that pure water dilution is obtained, make titanium oxide concentration become 10 weight % after, it is splashed in the glass culture dish container of external diameter 70mm, internal diameter 66mm, height 14mm, the about 48mL of capacity, so that become 1.75g/m by solid substance
2, launch so that it spreads on the whole culture dish equably.Utilize 110 ℃ drying machine that it is carried out 60 minutes drying, form photocatalyst film (oxidation titanium film), the culture dish of the band photocatalyst film that obtained is used as measure sample.
The above-mentioned culture dish that has photocatalyst film is put into 1 liter airbag as measure sample, and good seal, make become vacuum in the airbag after, enclose the mixed gas (oxygen: nitrogen=1: 4 (volume ratio)) of 600mL oxygen and nitrogen.By acetaldehyde by volume the concentration mode that becomes 200ppm in this airbag, also enclose 1vol% acetaldehyde, after the dark place of light makes it carry out 1 hour stable, begin rayed as light source with the luminescent lamp of selling on the market, carry out the decomposition reaction of acetaldehyde.Become 16000 luxs by the illumination on the film surface that makes measure sample culture dish is set, carry out rayed.After rayed begins, the gas in the airbag taken a sample in per 1.5 hours, utilize gas chromatograph (Shimadzu Seisakusho Ltd.'s system " GC-14A ") to measure the residual concentration of acetaldehyde.Then,, the concentration reduction of the acetaldehyde of every irradiation time is plotted on the logarithmic axis, the collinear slope that is obtained is obtained as the primary first-order equation velocity constant, estimate acetaldehyde decomposition ability according to this value with respect to irradiation time.The primary first-order equation velocity constant is big more, and acetaldehyde decomposition ability is good more, and in other words, photocatalytic activity is high more.
(Production Example--photocatalyst is synthetic)
Possess pH electrode be connected with this pH electrode, have and supply with 25 weight % ammoniacal liquor and adjust pH in the reaction vessel of the pH controller of constant function, inject ion exchanged water 30kg, the pH set(ting)value of pH controller is 4.In this reaction vessel, when the pH of the liquid in the container becomes lower than set(ting)value (4), begin to supply with ammoniacal liquor, and sustainable supply becomes set(ting)value up to the pH value.
By the 75kg titanyl sulfate is dissolved in the aqueous solution of titanyle sulfate that modulates in the 50kg ion exchanged water, under the refrigerative situation, add 35% the aquae hydrogenii dioxidi of 30kg, make mixing solutions.This mixing solutions is stirred with 42rpm on one side, with the speed of 530mL/ branch add in the above-mentioned reaction vessel that added ion exchanged water on one side, make itself and the ammoniacal liquor reaction that supplies in the reaction vessel by the pH controller, obtain resultant.At this moment, temperature of reaction is in 20 ℃～30 ℃ scope.After adding whole mixing solutionss, kept 1 hour, then, supply with 25 weight % ammoniacal liquor, become 4, obtain slurry, behind the slurry that filtration is obtained, use the water of 300kg to wash, obtain solid substance (filter cake) up to pH while stir the resultant that is obtained.The total amount that supplies to 25 weight % ammoniacal liquor in the reaction vessel is 90kg, is 2 times of aequum that are used for titanyl sulfate is converted to titanium hydroxide.
Then, with the above-mentioned solid substance that obtains of 2.3kg (filter cake), separately put in the stainless steel dish of 12 30cm * 40cm.These 12 dishes are put in the box drying machine (rising sun section length of schooling " ス one パ one テ Application プ オ one Block Application HP-60 ", internal volume: 216 liters), with 40m
3/ hour make the dry air circulation, 115 ℃ keep 5 hours down after, then under 250 ℃, carry out 5 hours drying, obtain BET surface-area 18.0m
2The dried powder of/g.Maximum water vapor pressure in the drying machine of this moment is 27.4kPa.Then, under air atmosphere, after 2 hours, cool to room temperature obtains the titanium dioxide powder as photocatalyst with 350 ℃ of dried powders that roasting was obtained.
(embodiment 1)
Dissolving 172.8g primary ammonium phosphate (with the pure medicine system of light, special grade chemical) in the ion exchanged water of 10.74kg, the modulation saline solution of ammonium phosphate.Photocatalyst (titanium dioxide powder) 4.0kg that is obtained in this saline solution of ammonium phosphate and the Production Example is put into media-agitation type dispersion machine (シ Application マ Le エ Application one プ ラ イ ゼ ス corporate system " ダ イ ノ one ミ Le KDL-PILOT A type "), zirconium white system bead with 4.2kg diameter 0.3mm is a dispersion medium, if stirring velocity is peripheral speed 8m/ second, carry out the treatment solution circulation by 3 liters of circulating fluid volumes, under the condition that adds up to 72 minutes treatment times, mix.The median size of the titanium oxide in the dispersion that this obtained is 420nm.Then, this dispersion is packed in the media-agitation type dispersion machine (コ ト Block キ skill development " ウ Le ト ラ ア ペ Star Network ス ミ Le "), zirconium white system bead with 13kg diameter 0.05mm is a dispersion medium, and establishing stirring velocity is peripheral speed 8m/ second (2000rpm), mixes 94 minutes.The median size of the titanium oxide in the dispersion that is obtained is 183nm thus.Further, 1 liter of the dispersion that obtained is taked into 1 liter with in the centrifugal settling pipe, carry out 30 minutes centrifugation with 1500rpm, remove the coarse grain composition, obtain the photocatalyst dispersoid of solid concentration 16.7 weight %, use ion exchanged water that it is diluted, become solid concentration 10 weight %.
The pH of the photocatalyst dispersoid that is obtained is 6.9, and acetaldehyde decomposition ability is 0.66 (l/h).Have, this photocatalyst dispersoid contains 4.3 weight part ammonium phosphate salts with respect to photocatalyst 100 weight parts again, does not contain the polymerizability silicon compound simultaneously, and polymerizability silicon compound/ammonium phosphate salt (weight ratio) is 0.
In addition, the median size of the titanium oxide in the photocatalyst dispersoid that is obtained is 155nm, and the viscosity of this photocatalyst dispersoid is 3mPas when measuring under 25 ℃ with BL type viscometer.And this median size and viscosity did not change after one month yet, and the photocatalyst dispersoid storage stability that is obtained is good.
(embodiment 2)
In the photocatalyst dispersoid of the solid concentration 16.7 weight % that 30g and embodiment 1 identical method obtains, add colloid silica (the daily output chemistry system " IPA-ST-ZL " of 0.42g as the polymerizability silicon compound, solid concentration 30 weight %), obtain photocatalyst dispersoid, it with after the ion exchanged water dilution, is become solid concentration 10 weight %.
The pH of the photocatalyst dispersoid that is obtained is 6.9, and acetaldehyde decomposition ability is 0.64 (l/h).Have again, this photocatalyst dispersoid, contain ammonium phosphate salt 4.3 weight parts with respect to photocatalyst 100 weight parts, and contain polymerizability silicon compound 2.5 weight parts with respect to photocatalyst 100 weight parts, polymerizability silicon compound/ammonium phosphate salt (weight ratio) is 0.57.
(embodiment 3)
In the photocatalyst dispersoid of the solid concentration 16.7 weight % that 30g and embodiment 1 identical method obtains, add colloid silica (the daily output chemistry system " IPA-ST-ZL " of 1.25g as the polymerizability silicon compound, solid concentration 30 weight %), obtain photocatalyst dispersoid, it with after the ion exchanged water dilution, is become solid concentration 10 weight %.
The pH of the photocatalyst dispersoid that is obtained is 6.9, and acetaldehyde decomposition ability is 0.64 (l/h).Have again, this photocatalyst dispersoid, contain ammonium phosphate salt 4.3 weight parts with respect to photocatalyst 100 weight parts, and contain polymerizability silicon compound 7.5 weight parts with respect to photocatalyst 100 weight parts, polymerizability silicon compound/ammonium phosphate salt (weight ratio) is 1.74.
(comparative example 1)
Dissolving 60% nitric acid (with the pure medicine system of light, special grade chemical) 157.5g in the 10.84kg ion exchanged water, the modulation aqueous nitric acid.Use this aqueous nitric acid to replace saline solution of ammonium phosphate, other is identical with embodiment 1, obtains photocatalyst dispersoid (amount of the nitric acid in the dispersion is 0.026 with respect to titanium oxide by weight).
The pH of the photocatalyst dispersoid that is obtained is 2.3, and acetaldehyde decomposition ability is 0.62 (l/h).Have, this photocatalyst dispersoid does not contain ammonium phosphate salt again, and does not contain the polymerizability silicon compound, and polymerizability silicon compound/ammonium phosphate salt (weight ratio) is 0.
The median size of the titanium oxide in the photocatalyst dispersoid that obtains is 132.7nm, and the viscosity of this photocatalyst dispersoid is measured as 3mPas with BL type viscometer under 25 ℃.
(comparative example 2)
In the photocatalyst dispersoid of the solid concentration 16.7 weight % that 30g and embodiment 1 identical method obtains, add colloid silica (the daily output chemistry system " IPA-ST-ZL " of 2.09g as the polymerizability silicon compound, solid concentration 30 weight %), obtain photocatalyst dispersoid, it with after the ion exchanged water dilution, is become solid concentration 10 weight %.
The pH of the photocatalyst dispersoid that is obtained is 6.9, and acetaldehyde decomposition ability is 0.60 (l/h).Have again, this photocatalyst dispersoid, contain ammonium phosphate salt 4.3 weight parts with respect to photocatalyst 100 weight parts, and contain polymerizability silicon compound 12.5 weight parts with respect to photocatalyst 100 weight parts, polymerizability silicon compound/ammonium phosphate salt (weight ratio) is 2.91.
(comparative example 3)
In the photocatalyst dispersoid of the solid concentration 16.7 weight % that 20g and embodiment 1 identical method obtains, add colloid silica (the daily output chemistry system " IPA-ST-ZL " of 5.57g as the polymerizability silicon compound, solid concentration 30 weight %), obtain photocatalyst dispersoid, it with after the ion exchanged water dilution, is become solid concentration 10 weight %.
The pH of the photocatalyst dispersoid that is obtained is 6.9, and acetaldehyde decomposition ability is 0.54 (l/h).Have again, this photocatalyst dispersoid, contain ammonium phosphate salt 4.3 weight parts with respect to photocatalyst 100 weight parts, and contain polymerizability silicon compound 50 weight parts with respect to photocatalyst 100 weight parts, polymerizability silicon compound/ammonium phosphate salt (weight ratio) is 11.62.
(comparative example 4)
The amount of primary ammonium phosphate is increased by 1 times, and other is identical with embodiment 1, obtains the photocatalyst dispersoid (it not being made solid concentration 10 weight % with the ion exchanged water dilution) of solid concentration 21.0 weight %, pH6.9.
Owing to gelation can occur when this photocatalyst dispersoid is at room temperature placed, so can't measure acetaldehyde decomposition ability.Have, this photocatalyst dispersoid contains ammonium phosphate salt 8.6 weight parts with respect to photocatalyst 100 weight parts, and does not contain the polymerizability silicon compound again, and polymerizability silicon compound/ammonium phosphate salt (weight ratio) is 0.
Hereinbefore, the result according to embodiment and comparative example can learn the following fact.Promptly, can learn because embodiment 1 is the photocatalyst dispersoid that does not contain the polymerizability silicon compound, embodiment 2 and embodiment 3 contain the photocatalyst dispersoid of polymerizability silicon compound in the scope that the present invention stipulates, so all can form the high coat film of photocatalytic activity.In more detail, as can be known, owing to do not contain the embodiment 1 of polymerizability silicon compound, its acetaldehyde decomposition ability height is so in order to obtain the more coat film of highlight catalytic active, the polymerizability silicon compound is few more good more when comparing embodiment 1 and embodiment 2 or embodiment 3.
In contrast, pH is an acidic region in the comparative example 1, and photocatalyst particles is disperseed, but acid for base material corrodibility and to worrying whiles such as danger of human body, photocatalytic activity is also weaker than photocatalyst dispersoid of the present invention.In addition, because being scopes of exceeding the present invention's regulation, comparative example 2 and comparative example 3 contain the photocatalyst dispersoid of polymerizability silicon compound, so the photocatalytic activity of the coat film that forms is poorer than all with embodiment.
In addition, contain the photocatalyst dispersoid of ammonium phosphate salt, rise, also at room temperature produce gelation so will cause viscosity because comparative example 4 is the scopes that exceed the present invention's regulation.
Claims (4)
1, a kind of photocatalyst dispersoid, comprise photocatalyst and water solvent, it is characterized in that, contain ammonium phosphate salt with respect to photocatalyst 100 weight parts with ratio less than 5 weight parts, and, do not contain the polymerizability silicon compound or contain the polymerizability silicon compound with respect to photocatalyst 100 weight parts in the ratio below 7.5 weight parts, polymerizability silicon compound/ammonium phosphate salt value by weight is below 5 simultaneously, and pH is 5～9.
2, photocatalyst dispersoid according to claim 1, photocatalyst is a titanium oxide.
3, photocatalyst dispersoid according to claim 1 and 2, photocatalyst shows photocatalytic activity to the rayed that luminescent lamp produces.
4, photocatalyst dispersoid according to claim 1 and 2, ammonium phosphate salt are any one or two kinds of primary ammonium phosphate and Secondary ammonium phosphate.
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| JP2006065690 | 2006-03-10 | ||
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101792618A (en) * | 2009-02-04 | 2010-08-04 | 住友化学株式会社 | The manufacture method of hydrophilic agent, hydrophilic agent and hydrophile function product |
| CN102942343A (en) * | 2012-11-20 | 2013-02-27 | 河海大学 | Method for manufacturing composite autoclaved aerated concrete loaded with Fe2O3 |
| CN103834289A (en) * | 2014-03-19 | 2014-06-04 | 安徽工业大学 | TiO2 photocatalysis coating for degrading formaldehyde gas and preparation method thereof |
| CN109158101A (en) * | 2018-10-11 | 2019-01-08 | 南通纺织丝绸产业技术研究院 | A kind of doping niobium, the tantalic acid titanium-based photochemical catalyst of vanadium, preparation method and application |
| CN109179559A (en) * | 2018-01-17 | 2019-01-11 | 赵兴海 | A kind of method of catalysis material catalytic degradation arylamine waste water |
-
2007
- 2007-03-06 TW TW096107697A patent/TW200738337A/en unknown
- 2007-03-07 KR KR1020070022460A patent/KR20070092627A/en not_active Application Discontinuation
- 2007-03-08 CN CNA200710092400XA patent/CN101033343A/en active Pending
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101792618A (en) * | 2009-02-04 | 2010-08-04 | 住友化学株式会社 | The manufacture method of hydrophilic agent, hydrophilic agent and hydrophile function product |
| CN102942343A (en) * | 2012-11-20 | 2013-02-27 | 河海大学 | Method for manufacturing composite autoclaved aerated concrete loaded with Fe2O3 |
| CN103834289A (en) * | 2014-03-19 | 2014-06-04 | 安徽工业大学 | TiO2 photocatalysis coating for degrading formaldehyde gas and preparation method thereof |
| CN103834289B (en) * | 2014-03-19 | 2015-09-23 | 安徽工业大学 | A kind of TiO for degradation of formaldehyde gas 2light catalyzed coating and preparation method thereof |
| CN109179559A (en) * | 2018-01-17 | 2019-01-11 | 赵兴海 | A kind of method of catalysis material catalytic degradation arylamine waste water |
| CN109158101A (en) * | 2018-10-11 | 2019-01-08 | 南通纺织丝绸产业技术研究院 | A kind of doping niobium, the tantalic acid titanium-based photochemical catalyst of vanadium, preparation method and application |
| CN109158101B (en) * | 2018-10-11 | 2021-09-17 | 南通纺织丝绸产业技术研究院 | Niobium and vanadium doped titanium-based tantalate photocatalyst, preparation method and application |
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|---|---|
| TW200738337A (en) | 2007-10-16 |
| KR20070092627A (en) | 2007-09-13 |
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