CN1683074A - Process for preparing visible light responding photo catalytic film layer - Google Patents
Process for preparing visible light responding photo catalytic film layer Download PDFInfo
- Publication number
- CN1683074A CN1683074A CN200510038095.7A CN200510038095A CN1683074A CN 1683074 A CN1683074 A CN 1683074A CN 200510038095 A CN200510038095 A CN 200510038095A CN 1683074 A CN1683074 A CN 1683074A
- Authority
- CN
- China
- Prior art keywords
- visible light
- film layer
- pucherite
- preparation
- bismuth
- 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
- 230000001699 photocatalysis Effects 0.000 title claims abstract description 26
- 238000004519 manufacturing process Methods 0.000 title description 9
- 239000000463 material Substances 0.000 claims abstract description 49
- 238000002360 preparation method Methods 0.000 claims abstract description 31
- 150000001875 compounds Chemical class 0.000 claims abstract description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 20
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 18
- 239000011941 photocatalyst Substances 0.000 claims abstract description 18
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims abstract description 16
- 229910052797 bismuth Inorganic materials 0.000 claims abstract description 16
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000000654 additive Substances 0.000 claims abstract description 7
- 230000000996 additive effect Effects 0.000 claims abstract description 7
- 239000008139 complexing agent Substances 0.000 claims abstract description 7
- 239000003960 organic solvent Substances 0.000 claims abstract description 5
- 238000003756 stirring Methods 0.000 claims abstract description 5
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims abstract description 3
- 229910017604 nitric acid Inorganic materials 0.000 claims abstract description 3
- 238000000034 method Methods 0.000 claims description 30
- 239000003054 catalyst Substances 0.000 claims description 18
- 239000002994 raw material Substances 0.000 claims description 18
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims description 16
- 239000000243 solution Substances 0.000 claims description 16
- 239000007864 aqueous solution Substances 0.000 claims description 15
- 239000011734 sodium Substances 0.000 claims description 14
- 229910052720 vanadium Inorganic materials 0.000 claims description 14
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims description 14
- 230000008569 process Effects 0.000 claims description 13
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 12
- 239000000843 powder Substances 0.000 claims description 12
- 229910000162 sodium phosphate Inorganic materials 0.000 claims description 12
- 239000001488 sodium phosphate Substances 0.000 claims description 12
- 235000011008 sodium phosphates Nutrition 0.000 claims description 12
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 claims description 12
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 11
- 229910052751 metal Inorganic materials 0.000 claims description 11
- 239000002184 metal Substances 0.000 claims description 11
- 239000000126 substance Substances 0.000 claims description 10
- 229910000397 disodium phosphate Inorganic materials 0.000 claims description 9
- 235000019800 disodium phosphate Nutrition 0.000 claims description 9
- 239000012153 distilled water Substances 0.000 claims description 9
- RXPAJWPEYBDXOG-UHFFFAOYSA-N hydron;methyl 4-methoxypyridine-2-carboxylate;chloride Chemical compound Cl.COC(=O)C1=CC(OC)=CC=N1 RXPAJWPEYBDXOG-UHFFFAOYSA-N 0.000 claims description 9
- 229910021645 metal ion Inorganic materials 0.000 claims description 9
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 9
- 150000002910 rare earth metals Chemical class 0.000 claims description 9
- CMZUMMUJMWNLFH-UHFFFAOYSA-N sodium metavanadate Chemical compound [Na+].[O-][V](=O)=O CMZUMMUJMWNLFH-UHFFFAOYSA-N 0.000 claims description 9
- PVGBHEUCHKGFQP-UHFFFAOYSA-N sodium;n-[5-amino-2-(4-aminophenyl)sulfonylphenyl]sulfonylacetamide Chemical compound [Na+].CC(=O)NS(=O)(=O)C1=CC(N)=CC=C1S(=O)(=O)C1=CC=C(N)C=C1 PVGBHEUCHKGFQP-UHFFFAOYSA-N 0.000 claims description 9
- 229910000166 zirconium phosphate Inorganic materials 0.000 claims description 9
- 239000004744 fabric Substances 0.000 claims description 8
- 239000011521 glass Substances 0.000 claims description 8
- 239000002245 particle Substances 0.000 claims description 8
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 7
- 238000007146 photocatalysis Methods 0.000 claims description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 6
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 6
- ZPWVASYFFYYZEW-UHFFFAOYSA-L dipotassium hydrogen phosphate Chemical compound [K+].[K+].OP([O-])([O-])=O ZPWVASYFFYYZEW-UHFFFAOYSA-L 0.000 claims description 6
- LWIHDJKSTIGBAC-UHFFFAOYSA-K tripotassium phosphate Chemical compound [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 claims description 6
- ODINCKMPIJJUCX-UHFFFAOYSA-N Calcium oxide Chemical compound [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 5
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 5
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 claims description 5
- JHXKRIRFYBPWGE-UHFFFAOYSA-K bismuth chloride Chemical compound Cl[Bi](Cl)Cl JHXKRIRFYBPWGE-UHFFFAOYSA-K 0.000 claims description 5
- -1 timber Substances 0.000 claims description 5
- 238000012876 topography Methods 0.000 claims description 5
- QYIGOGBGVKONDY-UHFFFAOYSA-N 1-(2-bromo-5-chlorophenyl)-3-methylpyrazole Chemical compound N1=C(C)C=CN1C1=CC(Cl)=CC=C1Br QYIGOGBGVKONDY-UHFFFAOYSA-N 0.000 claims description 4
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 4
- 239000011159 matrix material Substances 0.000 claims description 4
- 239000012528 membrane Substances 0.000 claims description 4
- 239000004033 plastic Substances 0.000 claims description 4
- 229920003023 plastic Polymers 0.000 claims description 4
- 229910052725 zinc Inorganic materials 0.000 claims description 4
- 239000011701 zinc Substances 0.000 claims description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 3
- 229910052684 Cerium Inorganic materials 0.000 claims description 3
- 229910052692 Dysprosium Inorganic materials 0.000 claims description 3
- 229910052691 Erbium Inorganic materials 0.000 claims description 3
- 229910052693 Europium Inorganic materials 0.000 claims description 3
- 229910052688 Gadolinium Inorganic materials 0.000 claims description 3
- 229910002651 NO3 Inorganic materials 0.000 claims description 3
- 229910052779 Neodymium Inorganic materials 0.000 claims description 3
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 3
- 229910052777 Praseodymium Inorganic materials 0.000 claims description 3
- 229910052772 Samarium Inorganic materials 0.000 claims description 3
- 229910000831 Steel Inorganic materials 0.000 claims description 3
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 3
- 229910052775 Thulium Inorganic materials 0.000 claims description 3
- 229910052769 Ytterbium Inorganic materials 0.000 claims description 3
- 229910021536 Zeolite Inorganic materials 0.000 claims description 3
- 239000004411 aluminium Substances 0.000 claims description 3
- 229910052782 aluminium Inorganic materials 0.000 claims description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 3
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 3
- 239000004327 boric acid Substances 0.000 claims description 3
- 229910052793 cadmium Inorganic materials 0.000 claims description 3
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- 239000000919 ceramic Substances 0.000 claims description 3
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 claims description 3
- 150000001805 chlorine compounds Chemical class 0.000 claims description 3
- 229910017052 cobalt Inorganic materials 0.000 claims description 3
- 239000010941 cobalt Substances 0.000 claims description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 3
- 239000004035 construction material Substances 0.000 claims description 3
- 230000008021 deposition Effects 0.000 claims description 3
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 3
- 235000019797 dipotassium phosphate Nutrition 0.000 claims description 3
- 229910000396 dipotassium phosphate Inorganic materials 0.000 claims description 3
- 239000000428 dust Substances 0.000 claims description 3
- KBQHZAAAGSGFKK-UHFFFAOYSA-N dysprosium atom Chemical compound [Dy] KBQHZAAAGSGFKK-UHFFFAOYSA-N 0.000 claims description 3
- UYAHIZSMUZPPFV-UHFFFAOYSA-N erbium Chemical compound [Er] UYAHIZSMUZPPFV-UHFFFAOYSA-N 0.000 claims description 3
- OGPBJKLSAFTDLK-UHFFFAOYSA-N europium atom Chemical compound [Eu] OGPBJKLSAFTDLK-UHFFFAOYSA-N 0.000 claims description 3
- UIWYJDYFSGRHKR-UHFFFAOYSA-N gadolinium atom Chemical compound [Gd] UIWYJDYFSGRHKR-UHFFFAOYSA-N 0.000 claims description 3
- 239000003365 glass fiber Substances 0.000 claims description 3
- UCNNJGDEJXIUCC-UHFFFAOYSA-L hydroxy(oxo)iron;iron Chemical compound [Fe].O[Fe]=O.O[Fe]=O UCNNJGDEJXIUCC-UHFFFAOYSA-L 0.000 claims description 3
- 229910052742 iron Inorganic materials 0.000 claims description 3
- 229910052746 lanthanum Inorganic materials 0.000 claims description 3
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims description 3
- 239000004579 marble Substances 0.000 claims description 3
- 150000004706 metal oxides Chemical class 0.000 claims description 3
- 239000010445 mica Substances 0.000 claims description 3
- 229910052618 mica group Inorganic materials 0.000 claims description 3
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 claims description 3
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- 239000011146 organic particle Substances 0.000 claims description 3
- 239000006174 pH buffer Substances 0.000 claims description 3
- 229910000160 potassium phosphate Inorganic materials 0.000 claims description 3
- 235000011009 potassium phosphates Nutrition 0.000 claims description 3
- PUDIUYLPXJFUGB-UHFFFAOYSA-N praseodymium atom Chemical compound [Pr] PUDIUYLPXJFUGB-UHFFFAOYSA-N 0.000 claims description 3
- 239000011347 resin Substances 0.000 claims description 3
- 229920005989 resin Polymers 0.000 claims description 3
- KZUNJOHGWZRPMI-UHFFFAOYSA-N samarium atom Chemical compound [Sm] KZUNJOHGWZRPMI-UHFFFAOYSA-N 0.000 claims description 3
- 239000010959 steel Substances 0.000 claims description 3
- NAWDYIZEMPQZHO-UHFFFAOYSA-N ytterbium Chemical compound [Yb] NAWDYIZEMPQZHO-UHFFFAOYSA-N 0.000 claims description 3
- 229910052727 yttrium Inorganic materials 0.000 claims description 3
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 claims description 3
- 239000010457 zeolite Substances 0.000 claims description 3
- 239000011324 bead Substances 0.000 claims description 2
- XGZRAKBCYZIBKP-UHFFFAOYSA-L disodium;dihydroxide Chemical compound [OH-].[OH-].[Na+].[Na+] XGZRAKBCYZIBKP-UHFFFAOYSA-L 0.000 claims description 2
- 230000001954 sterilising effect Effects 0.000 abstract description 7
- 239000000758 substrate Substances 0.000 abstract 2
- LSGOVYNHVSXFFJ-UHFFFAOYSA-N vanadate(3-) Chemical compound [O-][V]([O-])([O-])=O LSGOVYNHVSXFFJ-UHFFFAOYSA-N 0.000 abstract 2
- 230000001877 deodorizing effect Effects 0.000 abstract 1
- 239000007788 liquid Substances 0.000 description 23
- 238000005516 engineering process Methods 0.000 description 16
- 239000000049 pigment Substances 0.000 description 16
- 230000000694 effects Effects 0.000 description 10
- 238000000576 coating method Methods 0.000 description 6
- 238000005304 joining Methods 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- 239000004065 semiconductor Substances 0.000 description 5
- 238000004659 sterilization and disinfection Methods 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- 239000005357 flat glass Substances 0.000 description 4
- 239000011787 zinc oxide Substances 0.000 description 4
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 3
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 239000012876 carrier material Substances 0.000 description 3
- 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 3
- 230000008859 change Effects 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 238000000151 deposition Methods 0.000 description 3
- 125000000524 functional group Chemical group 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 231100000252 nontoxic Toxicity 0.000 description 3
- 230000003000 nontoxic effect Effects 0.000 description 3
- 239000002351 wastewater Substances 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 description 2
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 description 2
- 150000001622 bismuth compounds Chemical class 0.000 description 2
- DPSWNBLFKLUQTP-UHFFFAOYSA-N bismuth vanadium Chemical compound [V].[Bi] DPSWNBLFKLUQTP-UHFFFAOYSA-N 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000005229 chemical vapour deposition Methods 0.000 description 2
- 238000005253 cladding Methods 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 239000003651 drinking water Substances 0.000 description 2
- 235000020188 drinking water Nutrition 0.000 description 2
- 229960001484 edetic acid Drugs 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 230000004298 light response Effects 0.000 description 2
- 235000019837 monoammonium phosphate Nutrition 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 230000005855 radiation Effects 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000005995 Aluminium silicate Substances 0.000 description 1
- 241000894006 Bacteria Species 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 238000005411 Van der Waals force Methods 0.000 description 1
- 241000700605 Viruses Species 0.000 description 1
- AHUBLGVDRKDHAT-UHFFFAOYSA-N [Bi]=O.[Cl] Chemical compound [Bi]=O.[Cl] AHUBLGVDRKDHAT-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 230000000680 avirulence Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- CJOBVZJTOIVNNF-UHFFFAOYSA-N cadmium sulfide Chemical compound [Cd]=S CJOBVZJTOIVNNF-UHFFFAOYSA-N 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 210000000170 cell membrane Anatomy 0.000 description 1
- 238000007385 chemical modification Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 230000001186 cumulative effect Effects 0.000 description 1
- 238000005202 decontamination Methods 0.000 description 1
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- 239000013527 degreasing agent Substances 0.000 description 1
- 238000005237 degreasing agent Methods 0.000 description 1
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- 238000009826 distribution Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
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- 238000010304 firing Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000002440 industrial waste Substances 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
- MOUPNEIJQCETIW-UHFFFAOYSA-N lead chromate Chemical compound [Pb+2].[O-][Cr]([O-])(=O)=O MOUPNEIJQCETIW-UHFFFAOYSA-N 0.000 description 1
- 239000001035 lead pigment Substances 0.000 description 1
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- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000011824 nuclear material Substances 0.000 description 1
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- 239000010452 phosphate Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 229940072033 potash Drugs 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
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
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- 239000000523 sample Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 238000003746 solid phase reaction Methods 0.000 description 1
- 238000003836 solid-state method Methods 0.000 description 1
- 238000010671 solid-state reaction Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- 239000012855 volatile organic compound Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Landscapes
- Catalysts (AREA)
Abstract
The preparation process of visible light responding photocatalytic film layer features that the core or substrate to be coated is set inside water solution with water soluble inorganic or organic Bi compound and V compound, additive, complexing agent, NaOH, KOH and HNO3 while ultrasonically stirring, and after processing for 1-360 min, the core or substrate with obtained visible light responding photocatalytic bismuth vanadate film layer in the surface is taken out and washed with water or organic solvent. Thus obtained material with loaded bismuth vanadate photocatalyst has powerful sterilizing, deterging and deodorizing functions.
Description
Technical field
The present invention relates to a kind of technology of preparing of visible light responding photo catalytic film layer, especially relate to the easy manufacture technology of load pucherite photocatalyst film on various different materials.
Background technology
Pucherite is a kind of nontoxic novel yellow uitramarine, also is a kind of function admirable simultaneously, photochemical catalyst with very high visible light response activity.
Utilizing the photocatalysis technology environment purification is one " green technology ", has caused the generally attention of national governments, becomes the research focus of various countries academia and industrial circle.Photochemical catalyst can be removed harmful substance and sterilization in the air effectively under ultraviolet or radiation of visible light, water, carbon dioxide or other nontoxic material are resolved in VOCs in the air (pollutants such as formaldehyde, benzene series thing, sulfide, nitrogen oxide) direct oxidation, can destroy the cell membrane of various bacteriums efficiently, solidify the protein of various viruses, reach the purpose of sterilization.Environment such as family, office building, meeting room, indoor public places, hospital ward, child institute, school, microcomputer room and automobile, train, steamer, the aircraft vehicles now have been widely used in abroad.At present with the stable titanium dioxide (TiO of chemical property
2) be main research object, its wide industrial is used and is subjected to very big restriction, and the main problem that exists comprises: (1), quantum yield are low, and overall reaction rate is slower, are difficult to treating capacity is big and concentration is high industrial waste gas and waste water; (2), solar energy utilization ratio is low, because TiO
2Band structure determined its ultraviolet part that can only absorb in the sunshine can not absorb visible light.And sunshine medium ultraviolet light, the shared energy of visible light are about 4%, 43% respectively, and therefore exploitation has high quantum production rate, can are the keys that solves a difficult problem in the current photocatalysis technology by the high efficiency semiconductor photochemical catalyst of the excited by visible light in the solar spectrum.Utilize the research of photocatalyst treatment industrial and agricultural wastewater and deep purifying drinking water also just in the ascendant.Along with deepening continuously of research, believe in the near future and also will develop how better photocatalyst material, and other application function of finding photochemical catalyst.
Photochemical catalyst is in the application of reality, can be prepared into different shapes such as nanometer powder, fiber, porous material, block materials, also photochemical catalyst can be loaded on the difform carrier material, realize the multiple function of use of material or reach saving the photochemical catalyst purpose.Because powder can not be reused, also be difficult for reclaiming, and can't satisfy actual needs.Therefore general photocatalysis is prepared to film, loads on the difform carrier material and uses.
Bismuth vanadium pigments (orange-yellow) is a kind of yellow uitramarine, good visual effect, because various excellent performances such as tinting strength, tinting power, covering power, hear resistance, weatherability, chemical resistance, gloss retention, dispersiveness and rheological characteristic in all kinds of solvents are good, and be proved to be avirulence, become alternative chrome yellow, cadmium yellow, contained the product of lead pigments, at industrial circles such as pottery, coating and plastics just with extensively.The preparation method of bismuth vanadium pigments less expensive mainly contains synthesis by solid state reaction and aqueous solution coprecipitation method etc.But, limited its range of application because its price is very expensive.The just outer surface of particle that pigment reality can be utilized, and the particle kernel does not play a role, and can replace with kernel cheaply if promptly account for 30%～60% kernel portion of pigment cumulative volume, coat one deck pigment outside kernel, can improve the utilization rate of pigment greatly, reduce cost.At present the production method of coated pigment has two kinds of physics method and chemical methods.The physics method is to utilize relevant device and technology such as Centrifugal vibration mill, utilizes molecular separating force (Van der Waals force, hydrogen bond force) and electrostatic attraction between kernel and the pigment, and making it mutually, absorption becomes coated pigment.This method technological process is short, cost is low, do not have environmental pollution.But because the mutual absorption between production process center and the pigment is incomplete, be statistical distribution, so pigment mass instability of producing, in use, a little less than outer layer pigment and the interior internuclear active force, under high external force effect, outer layer pigment can come off from core surface gradually, make application performance descend even disappearance, chemical method is to utilize special-purpose covering to coat.Functional group more than 2 is arranged in each molecule of covering that adopts, and one of them functional group and kernel effect make covering firmly be adsorbed on core surface, another functional group and outer layer pigment effect.It fully is coated on above the kernel.After adopting chemisorbed, covering plays bridge linking effect between kernel and outer layer pigment, makes the active force increase of interior outer room, can satisfy requirement of actual application fully.But, owing to introduced covering aborning, make cost much larger than the physics method, and the technological process of production is long, environmental pollution is also more serious.Calcium carbonate, kaolin, silica are the inner nuclear materials of using always.The selection of covering is another key factor, and it must make outer layer pigment and kernel strong bonded, and covering is equivalent to kernel is carried out finishing, and good chemical modification can make the performance of kernel increase substantially.The internal nuclear mass of coating process requires very high, and requirement as usual is modified core surface, and the consumption of covering is reduced, and improves the coating quality.Another shortcoming of coating method is to handle powder material, and is powerless to the material of other shape and volume.Also have a kind of precipitation to coat method technology in the chemical method, the raw material that is about to bismuth-containing, vanadium dissolves in the solvent, and the material and the solution that will be coated mix, and adds precipitating reagent, makes pucherite be deposited in core surface, again through high-temperature process, obtains coating material.But high-temperature process energy consumption height, particle agglomeration is grown up, and also wants further broken, increases cost.
If can open up other application function of pucherite, improve technology of preparing, reduce the consumption of pucherite, reduce production costs, the application of pucherite material will constantly enlarge undoubtedly.On the other hand, the pucherite material has stronger visible absorption ability, and absorbing wavelength reaches 560nm, can absorb solar energy more than 10%.With respect to TiO
2What only can absorb solar energy is about 4%, and the ability that pucherite absorbs solar energy is greatly improved.Particularly pucherite can absorbing wavelength greater than the visible light of 400nm, this seems meaningful especially for the indoor environment that lacks ultraviolet light (optical wavelength is less than 400nm).Based on above factor, application present situation in conjunction with other photochemical catalyst and construction material, utilize pucherite to have stronger photocatalytic activity and itself can be as a kind of characteristics of eco-friendly yellow uitramarine, develop the load or the film preparing technology of new pucherite material, show urgent necessity and wide market application prospect.Load has many kinds in conjunction with the preparation method of firm pucherite thin layer, as laser pulse sputter, magnetron sputtering, sol-gal process, organic metal salt decomposition method, chemical vapour deposition (CVD) etc.These methods need expensive equipment, complex manufacturing process, scale and the output handled are limited, requirement height to raw material, the price height, to also need follow-up Technology for Heating Processing as sol-gal process, organic metal salt decomposition method etc. in addition with synthetic pucherite powder such as high temperature solid-state methods earlier, increase production cost.The more important thing is that these methods can not be handled the big load object of volume or surface, as door, glass pane etc.
In recent years, ultrasonic method is widely used in preparation and the synthetic scientific research field.Result of study shows, introduces in the solution with the ultrasonic wave of 10kHz～15kHz, has a large amount of bubbles and forms, grows, quick-fried then strong, produce " cavitation " phenomenon, and can in the extremely short time, in liquid, produce temperature, and air pressure reaches 1.7 * 10 up to 5000k
5The hot localised points of kpa produces catalytic action to chemical reaction, produces very big influence as the processing speed of growth, microstructure to film.
Inventor Zou Zhi is firm, Chen Yanfeng, leaf golden flower etc. have applied for composite oxide semiconductor photochemical catalyst pucherite (BiVO
4) be prepared into film photoelectric electrode, and be used to produce hydrogen and as battery electrode.Its application content is referring to " having visible light-responded porous membrane semiconductor photoelectrode and Optical Electro-Chemistry reaction unit and preparation ", and the application number of accepting is 200310106207.9.
What the inventor had applied for " contains bismuth composite oxide BiMO
*And Bi
*NO
*Type semiconductor light-catalyst and preparation and application " Patent project; application number: 200410041284.5; utilize the composite oxide semiconductor pucherite etc. of bismuth-containing to use, under ultraviolet or radiation of visible light, decompose harmful chemical, organic-biological matter and sterilization as photochemical catalyst.Wherein do not address and identical summary of the invention of the present invention.
Summary of the invention
The present invention seeks to: according to pucherite is a kind of nontoxic novel yellow uitramarine, also be a kind of function admirable simultaneously, have characteristics of the photochemical catalyst of very high visible light response activity, consider that there is expensive problem in simple use pucherite, invention present situation and vast market in conjunction with photochemical catalyst are just used prospect, and the easy manufacture technology of pucherite photocatalysis film layer is provided.In conjunction with related-art technology, adopt the simple heating deposition technique, utilize the cheap raw material of industry, only need common normal temperature and pressure aqueous solution firing equipment, can one-step method produce the pucherite thin layer, the pucherite photochemical catalyst is loaded on the various difform article.It is very simple to have technology for producing, and scale is changeable, and raw material is easy to get, characteristics with low cost.Utilize water miscible bismuth-containing compound, vanadium-containing compound, additive and multiple complexing agent to be raw material, be made into the certain density aqueous solution.
Purpose of the present invention is especially: the material of various desire loads is put into the aqueous solution of bismuth-containing compound, vanadium-containing compound, obtain the pucherite visible light responsive photocatalytic superficial layer of different-thickness, granularity, embedding cloth state and surface topography.Combine very firmly with matrix material thereby obtain superficial layer, have good photocatalytic activity, can reusable visible light responsive photocatalytic superficial layer.
The object of the present invention is achieved like this: the aqueous solution that the kernel or the backing material of various desire loads are put into bismuth-containing compound, vanadium-containing compound, at a certain temperature (generally from room temperature to 220 ℃) or simultaneously auxiliary ultrasonic stir, through different time (1-360min, especially after processing 30-200min), take out water or organic solvent and clean, obtain the pucherite visible light responsive photocatalytic superficial layer of different-thickness, granularity, embedding cloth state and surface topography.Ultrasonic wave can also play pulverization to fine particle, reduces particle size.Ultrasonic technology has very big auxiliary advantage to the preparation of pucherite cladding powder.
Particular content of the present invention is as follows:
1, the raw material of pucherite photocatalyst film layer preparation is that water miscible bismuth-containing compound is (as bismuth nitrate Bi (NO
3)
35H
2O, bismuth chloride BiCl
3, chlorine oxygen bismuth BiOClO
4Or bismuth acetate etc.), vanadium-containing compound is (as sodium vanadate NaVO
3, ammonium metavanadate NH
4VO
3Deng), additive is (as dibastic sodium phosphate NaH
2PO
4, sodium hydrogen phosphate Na
2HPO
4, potassium hydrogen phosphate KH
2PO
4, dipotassium hydrogen phosphate K
2HPO
4, boric acid H
3BO
3, sodium phosphate Na
3PO
3, potassium phosphate K
3PO
3, sodium carbonate Na
2CO
3Or potash K
2CO
3Deng, as the pH buffer) and complexing agent (as edta edta, citric acid C
6H
8O
75H
2O or Gly), NaOH NaOH, potassium hydroxide KOH, nitric acid HNO
3The raw material of preparation can also be various organic bismuth-containing compounds, vanadium-containing compound.
Adding as the material that mixes in addition, as rare earth, metal ion etc., is raw material with water-soluble nitrate, sulfate or chlorides such as Rare Earth Lanthanum, cerium, praseodymium, neodymium, samarium, europium, gadolinium, dysprosium, yttrium, thulium, ytterbium, erbium and iron, cobalt, nickel, zinc, cadmium, indiums.
2, the pucherite photocatalyst film of load one layer thickness on various different materials.According to different application requirements and carrier material, can be prepared into thickness is that nanoscale is to micron-sized thin layer.Its preparation process is the various raw materials described in the foregoing invention content 1, promptly utilizes water miscible bismuth-containing compound (bismuth nitrate Bi (NO
3)
35H
2O, bismuth chloride BiCl
3Deng), vanadium-containing compound (sodium vanadate NaVO
3, ammonium metavanadate NH
4VO
3Deng), additive (dibastic sodium phosphate NaH
2PO
4, sodium hydrogen phosphate Na
2HPO
4, ammonium dihydrogen phosphate (ADP) NH
4H
2PO
4, potassium hydrogen phosphate KH
2PO
4, dipotassium hydrogen phosphate K
2HPO
4, boric acid H
3BO
3, sodium phosphate Na
3PO
3, potassium phosphate K
3PO
3Deng, as the pH buffer) and multiple complexing agent (edta edta, citric acid C
6H
8O
75H
2O) be raw material, (scope of ratio is: the mol ratio of bismuth-containing compound and vanadium-containing compound is 1: 1-3.5 according to a certain percentage, the ratio of additive and complexing agent is an amount of, molar concentration is 0.01-0.5mol/L) join in the distilled water, adjust the pH value of solution with the NaOH aqueous solution, in whipping process,, obtain certain density clear solution with aqueous solution heating.Then the material of various desire loads is put into wherein, after the process processing of different time under certain 45～200 ℃ temperature, taking out water or organic solvent cleans, obtain the pucherite visible-light-responsive photocatalyst superficial layer of different-thickness, granularity, embedding cloth state and surface topography, can be used for the occasion of different needs.When load temperature during greater than 100 ℃, need pressurized equipment (under the hydrothermal condition), can accelerate the thin layer deposition velocity.
3, with the pucherite photocatalyst film layer of above-mentioned summary of the invention 1,2, cover on the different material surfaces, as bulk materials such as glass, steel plate, plastics, rubber, paper, timber, aluminium sheet, pottery, pottery, cloth, chemical fibres, and hollow metal ball, baton round, glass marble, foamed ceramics, glass fibre, perhaps by the made various difform article of these materials.
4,, cover on different powder (or bead, microballon, the whisker) material surface with the pucherite photocatalyst film layer of above-mentioned summary of the invention 1,2.As ZrO
2, SiO
2, Al
2O
3, TiO
2, ZnO, CaO, MgO, CaCO
3, functional material and construction material such as mica, zeolite, active carbon, lithopone, resin, metal dust, organic particle, magnetic metal or magnetic oxide particle.
5, with above-mentioned summary of the invention 1,2 described content and methods, the pucherite photochemical catalyst is deposited on the material of various porous membranes or nonporous film, as porous TiO
2, SiO
2, Al
2O
3, ZnO and other material.
6, in foregoing invention content 2, can add suitable rare earth or metal ion, make the pucherite photocatalyst film layer that contains the doping ion, obtain the pucherite thin layer of different surfaces pattern and performance.
7, the preparation of the auxiliary pucherite thin layer of microwave ultrasonic wave.Utilize the stirring action and the facilitation of ultrasonic wave, microwave,, pucherite photocatalysis film layer is coated on foregoing invention content 3,4, the 5 described various materials with above-mentioned summary of the invention 1,2 described content and methods.More suitable for the cladding powder material, can reduce the processing time, acquisition combines closely with matrix material, the fine and close more smooth thin layer in surface.
Characteristics of the present invention are:
The support materials that the pucherite photochemical catalyst is contained on these surfaces that the present invention obtains has very strong sterilization, sterilization, decontamination, deodorization functions.Be applicable to the advanced treating of purification, industrial and agricultural wastewater processing and the drinking water of indoor-outdoor air, and the sterilizing effect.Can also be used as photocatalysis solar energy electrode material, multi-use architecture coating etc.Technology of preparing flow process of the present invention is very simple, and equipment needed thereby is few, and scale is changeable, and raw material is easy to get, and is with low cost.Can promote the application of environmentally friendly pucherite photochemical catalyst in different field.With the preparation of the auxiliary pucherite thin layer of ultrasonic wave, can shorten the processing time, pucherite photocatalyst film layer combines closely with matrix or backing material, the surface is fine and close more smooth.
The specific embodiment
Embodiment 1
Preparation one deck pucherite photocatalyst film layer on sheet glass.Take by weighing a certain amount of bismuth nitrate Bi (NO respectively
3)
35H
2O and edta edta are dissolved in the distilled water, and joining concentration then is the dibastic sodium phosphate NaH of 0.1mol/L
2PO
4, sodium hydrogen phosphate Na
2HPO
4In the cushioning liquid, as A liquid; Again with sodium vanadate NaVO
3Joining concentration is the dibastic sodium phosphate NaH of 0.1mol/L
2PO
4, sodium hydrogen phosphate Na
2HPO
4Cushioning liquid is as B liquid; Control adding speed joins B liquid in the A liquid, and be controlled at bismuth nitrate: ethylenediamine tetra-acetic acid: sodium vanadate is 1: 2～3: 2～3 (mol ratios), is about the pH=7 of NaOH aqueous solution adjustment solution of 1mol/L with concentration.In whipping process,, obtain certain density clear solution, as C liquid with aqueous solution heating.To vertically be placed in the above-mentioned C liquid through the sheet glass that ultrasonic clear Xian such as soda acid, distilled water, ethanol, acetone cross then, under certain temperature (90 ℃) through 3 hours processing after, taking-up is cleaned with distilled water, and drying is after XRD determining, and obtaining orange-yellow surface film layer is pucherite.
Bismuth compound is selected bismuth chloride BiCl for use
3Or bismuth acetate etc., vanadium-containing compound are selected ammonium metavanadate NH for use
4VO
3And same effect is arranged.
Adopt summary of the invention 1,2 described other raw materials and change technological parameter, utilize above-mentioned preparation method on summary of the invention 3,4,5 described materials, also can obtain pucherite surface film layer.
With Ultrasonic Wave-Assisted Preparation pucherite thin layer, the time foreshortens to 30min.The microwave ultrasonic wave Assisted Preparation then will be through 0.2-3 hour processing under the room temperature.
Backing material can be selected bulk materials such as glass, steel plate, plastics, rubber, paper, timber, aluminium sheet, pottery, pottery, cloth, chemical fibre, and hollow metal ball, baton round, glass marble, foamed ceramics, glass fibre etc. are unqualified.Also can be deposited on the material of various porous membranes or nonporous film, as porous TiO
2, SiO
2, Al
2O
3, ZnO and other material.
Embodiment 2
The preparation of the pucherite photocatalyst film layer of rare earth doped or metal ion.Take by weighing a certain amount of bismuth nitrate Bi (NO respectively
3)
35H
2O, cerous nitrate Ce (NO
3)
36H
2O and edta edta are dissolved in edta edta in the distilled water earlier, and then add Bi (NO
3)
35H
2O, cerous nitrate Ce (NO
3)
36H
2O, then joining concentration is the dibastic sodium phosphate NaH of 0.1mol/L
2PO
4, sodium hydrogen phosphate Na
2HPO
4In the cushioning liquid, as A liquid; Again with sodium vanadate NaVO
3Joining concentration is the dibastic sodium phosphate NaH of 0.1mol/L
2PO
4, sodium hydrogen phosphate Na
2HPO
4Cushioning liquid is as B liquid; Control adding speed joins B liquid in the A liquid, and be controlled at (bismuth nitrate+cerous nitrate): citric acid: sodium vanadate is 1: 1.5～3: 1.5～3, is about pH=6.5～8 of NaOH aqueous solution adjustment solution of 1mol/L with concentration.In whipping process,, obtain certain density clear solution, as C liquid with aqueous solution heating.
Get one of simple glass sheet, handled 5 minutes down at 50 ℃ with phosphate type alkalescent degreasing agent solution earlier,, add hydrogen peroxide again and handle a moment, take out with ultrasonic clear Xian such as distilled water, ethanol, acetone, and dry up with nitrogen then at 1: 1 ammoniacal liquor digestion.The sheet glass of handling is joined in the above-mentioned C liquid, can on sheet glass, make the pucherite surface film layer of mix various rare earths or metal ion.
Adopt summary of the invention 1,2 described other raw materials and change technological parameter, utilize above-mentioned preparation method on summary of the invention 3,4,5 described materials, also can obtain the to mix pucherite surface film layer of various rare earths or metal ion.
Embodiment 3
The surface coats the preparation of the nano zine oxide of pucherite photocatalyst film layer.The preparation of solution such as embodiment 1 promptly take by weighing a certain amount of bismuth nitrate Bi (NO respectively
3)
35H
2O and edta edta are dissolved in the distilled water, and joining concentration then is the dibastic sodium phosphate NaH of 0.1mol/L
2PO
4, sodium hydrogen phosphate Na
2HPO
4In the cushioning liquid, as A liquid; Again with sodium vanadate NaVO
3Joining concentration is the dibastic sodium phosphate NaH of 0.1mol/L
2PO
4, sodium hydrogen phosphate Na
2HPO
4Cushioning liquid is as B liquid; Control adding speed joins B liquid in the A liquid, and be controlled at bismuth nitrate: ethylenediamine tetra-acetic acid: sodium vanadate is 1: 2～3: 2～3, is about the pH=7 of NaOH aqueous solution adjustment solution of 1mol/L with concentration.The Zinc oxide powder that adds a certain amount of particle mean size again and be 60 nanometers is placed in the ultrasonic cleaner of band heater in solution, and the beginning heat temperature raising is opened ultrasonic agitation simultaneously, handles under 80 ℃ temperature 1～3 hour, obtains yellow powder.With solution and powder separation, use alcohol and distilled water cyclic washing powder repeatedly, at last with spray-dried, obtain the nano oxidized zinc product that the surface coats pucherite photocatalyst film layer.
Adopt summary of the invention 1,2 described other raw materials and change technological parameter, utilize above-mentioned preparation method on summary of the invention 3,4,5 described materials, also can obtain pucherite surface film layer, the pucherite surface film layer of perhaps mix various rare earths or metal ion.Bismuth compound is selected bismuth chloride BiCl for use
3Or bismuth acetate etc., vanadium-containing compound are selected ammonium metavanadate NH for use
4VO
3And same effect is arranged.
Different powder load body such as ZrO
2, SiO
2, Al
2O
3, TiO
2, ZnO, CaO, MgO, CaCO
3, functional material such as mica, zeolite, active carbon, lithopone, resin, metal dust, organic particle, magnetic metal or magnetic oxide particle has identical area load effect.
When load temperature during greater than 100 ℃, need in bearing device, carry out, can accelerate the thin layer deposition velocity.Prepare the pucherite thin layer with ultrasonic wave, microwave are auxiliary, the time more shortens.Ultrasonic unit can use the probe of supersonic wave cleaning machine to insert in the container of solution, or transmits ultrasonic energy at wall; Heating using microwave is rapid, and the effect that promotes chemical reaction is arranged
Can add suitable rare earth or metal ion, make the pucherite photocatalyst film layer that contains the doping ion, obtain the pucherite thin layer of different surfaces pattern and performance.
Adding as the material that mixes in addition, as rare earth, metal ion etc., is raw material with water-soluble nitrate, sulfate or chlorides such as Rare Earth Lanthanum, cerium, praseodymium, neodymium, samarium, europium, gadolinium, dysprosium, yttrium, thulium, ytterbium, erbium and iron, cobalt, nickel, zinc, cadmium, indiums.Addition is less, can improve catalytic performance.
Claims (8)
1, the preparation method of visible light responding photo catalytic film layer is characterized in that desiring to be coated with the aqueous solution that negative kernel or backing material are put into bismuth-containing compound, vanadium-containing compound with various, and raw material is that water miscible bismuth-containing compound is (as bismuth nitrate Bi (NO
3)
35H
2O, bismuth chloride BiCl
3Or bismuth acetate etc.), vanadium-containing compound is (as sodium vanadate NaVO
3, ammonium metavanadate NH
4VO
3Deng), additive is (as dibastic sodium phosphate NaH
2PO
4, sodium hydrogen phosphate Na
2HPO
4, potassium hydrogen phosphate KH
2PO
4, dipotassium hydrogen phosphate K
2HPO
4, boric acid H
3BO
3, sodium phosphate Na
3PO
3, potassium phosphate K
3PO
3, Na
2CO
3Or K
2CO
3Deng, as the pH buffer) and complexing agent (as edta edta, citric acid C
6H
8O
75H
2O or Gly), NaOH NaOH, potassium hydroxide KOH, nitric acid HNO
3The raw material of preparation can also be various organic bismuth-containing compounds, vanadium-containing compound; Under the condition of room temperature to 220 ℃ or simultaneously auxiliary ultrasonic stirs, and through after the processing of 1-360min, takes out water or organic solvent and cleans, and obtains the pucherite visible light responsive photocatalytic superficial layer of different-thickness, granularity, embedding cloth state and surface topography.
2, by the preparation method of the described visible light responding photo catalytic film layer of claim 1, it is characterized in that adding in addition as the material that mixes, as rare earth, metal ion etc., be raw material with water-soluble nitrate, sulfate or chlorides such as Rare Earth Lanthanum, cerium, praseodymium, neodymium, samarium, europium, gadolinium, dysprosium, yttrium, thulium, ytterbium, erbium and iron, cobalt, nickel, zinc, cadmium, indiums.
3,, it is characterized in that the pucherite photocatalyst film of load one layer thickness on various different materials by the preparation method of the described visible light responding photo catalytic film layer of claim 1.At bulk materials such as glass, steel plate, plastics, rubber, paper, timber, aluminium sheet, pottery, pottery, cloth, chemical fibres, and hollow metal ball, baton round, glass marble, foamed ceramics, glass fibre, perhaps by the made various difform article of this material.Being prepared into thickness is that nanoscale is to micron-sized thin layer.
4, by the preparation method of the described visible light responding photo catalytic film layer of claim 1, the mol ratio that it is characterized in that bismuth-containing compound and vanadium-containing compound is 1: 1-3.5, the ratio of additive and complexing agent is an amount of, molar concentration is that 0.01-0.5mol/L joins in the distilled water, adjust the pH of solution with the NaOH aqueous solution, in whipping process,, obtain certain density clear solution with aqueous solution heating; Then the material of various desire loads is put into wherein, after the process processing of different time under certain 45～200 ℃ temperature, taking out water or organic solvent cleans, obtain the pucherite visible-light-responsive photocatalyst superficial layer of different-thickness, granularity, embedding cloth state and surface topography, can be used for the occasion of different needs.
5, by the preparation method of the described visible light responding photo catalytic film layer of claim 1, it is characterized in that needing pressurized equipment (under the hydrothermal condition) when load temperature during greater than 100 ℃, can accelerate the thin layer deposition velocity.
6,, it is characterized in that covering on different powder (or bead, microballon, the whisker) material surface by the preparation method of the described visible light responding photo catalytic film layer of claim 1.As ZrO
2, SiO
2, Al
2O
3, TiO
2, ZnO, CaO, MgO, CaCO
3, functional material and construction material such as mica, zeolite, active carbon, lithopone, resin, metal dust, organic particle, magnetic metal or magnetic oxide particle.
7,, it is characterized in that the pucherite photochemical catalyst is deposited on the material of various porous membranes or nonporous film, as porous TiO by the preparation method of the described visible light responding photo catalytic film layer of claim 1
2, SiO
2, Al
2O
3, ZnO and other material.
8, by the preparation method of claim 1,2 or 7 described visible light responding photo catalytic film layers, it is characterized in that utilizing the stirring and the facilitation of ultrasonic wave, microwave, pucherite photocatalysis film layer is coated on kernel or the backing material, and acquisition combines closely with matrix material, the fine and close more smooth thin layer in surface.
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