CN101733133A - Titanium dioxide photocatalyst with coating layer coated on surface and preparation method thereof - Google Patents
Titanium dioxide photocatalyst with coating layer coated on surface and preparation method thereof Download PDFInfo
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- CN101733133A CN101733133A CN200910155274A CN200910155274A CN101733133A CN 101733133 A CN101733133 A CN 101733133A CN 200910155274 A CN200910155274 A CN 200910155274A CN 200910155274 A CN200910155274 A CN 200910155274A CN 101733133 A CN101733133 A CN 101733133A
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- titanium dioxide
- fluoride
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 211
- 239000004408 titanium dioxide Substances 0.000 title claims abstract description 101
- 238000002360 preparation method Methods 0.000 title claims abstract description 27
- 239000011247 coating layer Substances 0.000 title claims abstract description 17
- 239000011941 photocatalyst Substances 0.000 title abstract 4
- 239000000843 powder Substances 0.000 claims abstract description 29
- 229910019142 PO4 Inorganic materials 0.000 claims abstract description 28
- 239000010452 phosphate Substances 0.000 claims abstract description 28
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 claims abstract description 27
- 239000002245 particle Substances 0.000 claims abstract description 22
- 229910001512 metal fluoride Inorganic materials 0.000 claims abstract description 20
- 238000000034 method Methods 0.000 claims abstract description 19
- 229910052587 fluorapatite Inorganic materials 0.000 claims abstract description 17
- 229940077441 fluorapatite Drugs 0.000 claims abstract description 17
- VSIIXMUUUJUKCM-UHFFFAOYSA-D pentacalcium;fluoride;triphosphate Chemical compound [F-].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O VSIIXMUUUJUKCM-UHFFFAOYSA-D 0.000 claims abstract description 17
- 239000003054 catalyst Substances 0.000 claims description 65
- 230000003287 optical effect Effects 0.000 claims description 34
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 33
- 239000007864 aqueous solution Substances 0.000 claims description 30
- -1 cation salt Chemical class 0.000 claims description 19
- 238000001914 filtration Methods 0.000 claims description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 17
- 239000000243 solution Substances 0.000 claims description 16
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 15
- 229910021645 metal ion Inorganic materials 0.000 claims description 14
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 14
- 229910052751 metal Inorganic materials 0.000 claims description 13
- 239000002184 metal Substances 0.000 claims description 13
- 239000003153 chemical reaction reagent Substances 0.000 claims description 12
- 239000003795 chemical substances by application Substances 0.000 claims description 12
- 230000003750 conditioning effect Effects 0.000 claims description 12
- 230000001376 precipitating effect Effects 0.000 claims description 12
- 239000000376 reactant Substances 0.000 claims description 12
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 claims description 12
- 238000003483 aging Methods 0.000 claims description 11
- 230000032683 aging Effects 0.000 claims description 11
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 11
- 239000013049 sediment Substances 0.000 claims description 10
- 238000005406 washing Methods 0.000 claims description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- 238000009835 boiling Methods 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 claims description 4
- NROKBHXJSPEDAR-UHFFFAOYSA-M potassium fluoride Chemical compound [F-].[K+] NROKBHXJSPEDAR-UHFFFAOYSA-M 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- FQKMRXHEIPOETF-UHFFFAOYSA-N F.OP(O)(O)=O Chemical compound F.OP(O)(O)=O FQKMRXHEIPOETF-UHFFFAOYSA-N 0.000 claims description 3
- 239000011775 sodium fluoride Substances 0.000 claims description 3
- 235000013024 sodium fluoride Nutrition 0.000 claims description 3
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 claims description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 2
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 2
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 claims description 2
- 229910000388 diammonium phosphate Inorganic materials 0.000 claims description 2
- 235000019838 diammonium phosphate Nutrition 0.000 claims description 2
- ZPWVASYFFYYZEW-UHFFFAOYSA-L dipotassium hydrogen phosphate Chemical compound [K+].[K+].OP([O-])([O-])=O ZPWVASYFFYYZEW-UHFFFAOYSA-L 0.000 claims description 2
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 claims description 2
- 229910000397 disodium phosphate Inorganic materials 0.000 claims description 2
- 235000019800 disodium phosphate Nutrition 0.000 claims description 2
- 150000002221 fluorine Chemical class 0.000 claims description 2
- 229910052747 lanthanoid Inorganic materials 0.000 claims description 2
- 150000002602 lanthanoids Chemical class 0.000 claims description 2
- 239000011698 potassium fluoride Substances 0.000 claims description 2
- 235000003270 potassium fluoride Nutrition 0.000 claims description 2
- 230000001699 photocatalysis Effects 0.000 abstract description 27
- 230000003197 catalytic effect Effects 0.000 abstract description 12
- 239000013078 crystal Substances 0.000 abstract description 6
- 239000000463 material Substances 0.000 abstract description 4
- 239000000203 mixture Substances 0.000 abstract description 4
- 239000002994 raw material Substances 0.000 abstract description 4
- 238000001179 sorption measurement Methods 0.000 abstract description 3
- 239000002957 persistent organic pollutant Substances 0.000 abstract description 2
- 239000002243 precursor Substances 0.000 abstract 2
- 239000011248 coating agent Substances 0.000 abstract 1
- 238000000576 coating method Methods 0.000 abstract 1
- 238000000151 deposition Methods 0.000 abstract 1
- 239000000126 substance Substances 0.000 abstract 1
- 239000011575 calcium Substances 0.000 description 22
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 15
- 239000012071 phase Substances 0.000 description 14
- 239000000725 suspension Substances 0.000 description 14
- 230000015556 catabolic process Effects 0.000 description 13
- 238000006731 degradation reaction Methods 0.000 description 13
- 238000011156 evaluation Methods 0.000 description 13
- 238000005253 cladding Methods 0.000 description 11
- 230000003647 oxidation Effects 0.000 description 11
- 238000007254 oxidation reaction Methods 0.000 description 11
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 10
- 239000010936 titanium Substances 0.000 description 10
- 229910052719 titanium Inorganic materials 0.000 description 10
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 9
- 238000001816 cooling Methods 0.000 description 9
- 238000005516 engineering process Methods 0.000 description 8
- 238000007146 photocatalysis Methods 0.000 description 8
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- 239000011259 mixed solution Substances 0.000 description 6
- 206010013786 Dry skin Diseases 0.000 description 5
- 239000002253 acid Substances 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- 238000006555 catalytic reaction Methods 0.000 description 4
- ISPYQTSUDJAMAB-UHFFFAOYSA-N 2-chlorophenol Chemical compound OC1=CC=CC=C1Cl ISPYQTSUDJAMAB-UHFFFAOYSA-N 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 239000000706 filtrate Substances 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 2
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 description 2
- 239000001506 calcium phosphate Substances 0.000 description 2
- 229910000389 calcium phosphate Inorganic materials 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 239000004020 conductor Substances 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 230000005284 excitation Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 238000004128 high performance liquid chromatography Methods 0.000 description 2
- 239000010842 industrial wastewater Substances 0.000 description 2
- 229910001506 inorganic fluoride Inorganic materials 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 238000009281 ultraviolet germicidal irradiation Methods 0.000 description 2
- 238000007704 wet chemistry method Methods 0.000 description 2
- HNSDLXPSAYFUHK-UHFFFAOYSA-N 1,4-bis(2-ethylhexyl) sulfosuccinate Chemical compound CCCCC(CC)COC(=O)CC(S(O)(=O)=O)C(=O)OCC(CC)CCCC HNSDLXPSAYFUHK-UHFFFAOYSA-N 0.000 description 1
- RZVAJINKPMORJF-UHFFFAOYSA-N Acetaminophen Chemical compound CC(=O)NC1=CC=C(O)C=C1 RZVAJINKPMORJF-UHFFFAOYSA-N 0.000 description 1
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- 241001125671 Eretmochelys imbricata Species 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-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
- 150000001412 amines Chemical class 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 239000000987 azo dye Substances 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 230000003749 cleanliness Effects 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 150000004673 fluoride salts Chemical class 0.000 description 1
- 150000002222 fluorine compounds Chemical class 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- IDIJOAIHTRIPRC-UHFFFAOYSA-J hexaaluminum;sodium;2,2,4,4,6,6,8,8,10,10,12,12-dodecaoxido-1,3,5,7,9,11-hexaoxa-2,4,6,8,10,12-hexasilacyclododecane;iron(2+);triborate;tetrahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[Na+].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[Fe+2].[Fe+2].[Fe+2].[O-]B([O-])[O-].[O-]B([O-])[O-].[O-]B([O-])[O-].[O-][Si]1([O-])O[Si]([O-])([O-])O[Si]([O-])([O-])O[Si]([O-])([O-])O[Si]([O-])([O-])O[Si]([O-])([O-])O1 IDIJOAIHTRIPRC-UHFFFAOYSA-J 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 231100001240 inorganic pollutant Toxicity 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical compound [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000013507 mapping Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 230000007096 poisonous effect Effects 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000005297 pyrex Substances 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 229910000246 schorl Inorganic materials 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
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Classifications
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/30—Wastewater or sewage treatment systems using renewable energies
- Y02W10/37—Wastewater or sewage treatment systems using renewable energies using solar energy
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Abstract
The invention provides a titanium dioxide photocatalyst with a coating layer coated on a surface, which comprises a titanium dioxide powder particle, wherein a fluoride coating layer, a fluoride-phosphate coating layer or a fluorapatite coating layer is arranged outside the titanium dioxide powder particle. Compared with an ordinary titanium dioxide powder particle, the photocatalytic speed is markedly increased. The invention also provides a preparation method of the titanium dioxide photocatalyst with the coating layer coated on the surface, which comprises the following steps of: depositing titanium dioxide as a precursor and a metal fluoride, a fluoride-phosphate mixture or fluorapatite as a coating material on the surface of the titanium dioxide powder particle by using a wet chemical method and preparing a product under the condition of not changing the crystal structure, the crystal phase composition and the average particle diameter of the titanium dioxide as the precursor. The titanium dioxide photocatalyst has low cost of the used raw materials, simple equipment and easy operation; compared with the pure titanium dioxide, the ultraviolet light catalytic activity of the obtained product is markedly improved, and meanwhile, the adsorption capacity for an organic pollutant is also enhanced.
Description
Technical field
The present invention relates to a kind of titanium deoxide catalyst and preparation method thereof, belong to catalysis technical field, more concrete is to the invention provides a kind of surface to contain metal fluoride clad, the common phosphate clad of metal fluoride or fluor-apatite clad and have nano TiO 2 powder photochemical catalyst of high catalytic activity and preparation method thereof.
Background technology
21 century, energy shortage and environmental pollution are increasingly serious, the subject matter that has become the world today and faced.Therefore, national governments, scientist and technical staff actively take measures, and are tackled.In many processing methods, the conductor photocatalysis technology is especially noticeable, it can directly utilize the ultraviolet light of the various approach that comprise sunshine, just can make various organic or inorganic pollutants that thoroughly degraded and mineralising take place at ambient temperature, thereby reach the purpose of removing environmental contaminants.This technology have energy consumption low, easy to operate, remove characteristics such as cleanliness height, especially to some special pollutants, photocatalysis technology has more the incomparable advantage of other technologies, and non-secondary pollution.At present, photocatalysis technology has become a focus in various countries' high-tech competition, is with a wide range of applications.
1972, Fujishima and Honda found, are subjected to the red schorl phase titanium dioxide monocrystalline electrode of ultraviolet excitation can water be decomposed.1976, discoveries such as Carey were subjected to the titanium dioxide of ultraviolet excitation that poisonous biphenyl and chlordiphenyl are degraded.After 1 year, Frank and Bard find the cyanide of titanium dioxide in can photocatalytic degradation water, and have proposed photocatalysis technology is applied to the suggestion of the depollution of environment.After this, curb environmental pollution and become in the conductor photocatalysis field active research direction the most.In numerous semiconductor light-catalysts, titanium dioxide is best for this reason so far photochemical catalyst, and relevant its research is in core status always.Titanium dioxide not only has advantages of high catalytic activity and stronger oxidability, and its biology, chemistry and photochemical stability height, and itself is nontoxic and inexpensive.
To the research of titanium dioxide optical catalyst, carried out 30 or 40 years, still in the ascendant at present.It is found that, the crystalline form by changing TiO 2 particles, specific surface, degree of crystallinity etc., and it is carried out anion and cation doping or finishing etc., can improve the photocatalytic activity of titanium dioxide.But the obtained efficient of optically catalytic TiO 2 can't satisfy the requirement of industrial applications at present.2000, discoveries such as Minero added sodium fluoride in the titanium dioxide water slurry of acidity, can significantly improve the photocatalytic speed of degradation of phenol in the titanium dioxide photocatalysis body system.Subsequently, other researchers are also finding similar phenomenon aspect the organic matters such as optically catalytic TiO 2 degraded chlorophenol, organic acid, benzene, amine, azo dyes, cyanuric acid.In addition, this method also can improve the efficient that optically catalytic TiO 2 selective oxidation benzene generates phenol, selective oxidation cyclohexane generation several ketone of ring and encircles important chemical reactions such as several alcohol.This shows, add fluorine ion in the titanium dioxide water slurry, is an important means that improves optically catalytic TiO 2 efficient.Yet fluorine ion is as a kind of important pollutant of water body, and there is strict emission limit set in country to it.The relevant laws and regulations regulation, the content of fluoride ion in the industrial wastewater must not be greater than 0.5mM.Therefore, fluorine ion is immobilized in the TiO 2 particles surface, make it bring into play above-mentioned effect, become the problem that needs solution.
Reference that the present invention adopts:
M.R.Hoffmann,S.T.Martin,W.Choi,D.W.Bahnemann,Chem.Rev.1995,95,69-96;
C.Minero,G.Mariella,V.Maurino,E.Pelizzetti,Langmuir?2000,16,2632-2641.;
Y.Xu,K.Lv,Z.Xiong,W.Leng,W.Du,D.Liu,X.Xue,J.Phys.Chem.C?2007,111,19024-19032;
N.Senamaud,D.Bernache-Assollant,E.Champion,M.Heughebaert,C.Ray,Solid?StateIonics?1997,101-103,1357-1362。
Summary of the invention
The titanium dioxide optical catalyst that the object of the present invention is to provide a kind of surface to be coated with coating layer with high catalytic activity.Purpose of the present invention realizes by following technical measures:
It comprises the titanium dioxide powder particle, and described titanium dioxide powder particle is provided with fluoride clad, fluoride phosphate clad or fluor-apatite clad altogether outward.
By above technical scheme, the titanium dioxide powder particle that the present invention is common relatively, photocatalytic speed significantly improves.
The present invention also aims to provide the preparation method of the titanium dioxide optical catalyst that the surface is coated with coating layer, purpose of the present invention realizes by following technical measures:
The present invention is presoma with titanium dioxide, with metal fluoride, fluoride-phosphate mixt or fluor-apatite is clad material, method by wet chemistry is deposited on the titanium dioxide powder particle surface, prepares the titanium dioxide optical catalyst that the surface is coated with coating layer under the situation of the crystal structure that does not change presoma titanium dioxide, crystalline phase composition and average grain diameter.
The cost of material that the present invention uses is cheap, and equipment is simple, easy operating; The gained photochemical catalyst is than simple titanium dioxide, and its ultraviolet catalytic is active obviously to be improved, and simultaneously the organic pollutant adsorption ability is also promoted to some extent.
Description of drawings
Fig. 1 is the structural representation of the surperficial titanium dioxide optical catalyst that is coated with coating layer;
Fig. 2 is that the X ray diffracting spectrum of embodiment 1,2 is (with pure TiO
2Relatively);
Fig. 3 is that the blue Miu Er adsorption isotherm of 1,2 pairs of organic pollutions of embodiment (2, the 4-chlorophenesic acid) is (with pure TiO
2Relatively);
Fig. 4 is that the ultraviolet degradation phenol curve of embodiment 1,2,3 is (with pure TiO
2Relatively);
Fig. 5 carries out above-mentioned light-catalyzed reaction after 2 hours for embodiment 1,2,3, fluorinion concentration in the solution (fluorine ion discharge capacity limitation standard GB in the industrial wastewater being compared with country).
The specific embodiment
With reference to accompanying drawing 1.The titanium dioxide optical catalyst that the present invention is coated with coating layer for a kind of surface, it comprises titanium dioxide powder particle 1, described titanium dioxide powder particle is provided with clad 2 outward, and described clad is metal fluoride clad, metal fluoride phosphate clad or fluor-apatite clad altogether.
This composite catalyst has the crystal structure similar with the titanium dioxide raw material, crystalline phase is formed and average grain diameter, but it has higher ultraviolet light photocatalysis activity.The present invention is at the direct coated inorganic fluoride of the titanium dioxide powder particle surface of commodity that are easy to get or artificial preparation, realized fluorine element immobilized in the titanium dioxide optical catalyst particle surface; The gained catalyst has very high photocatalytic activity, and the fluorinion concentration of stripping is lower than national limitation standard in water simultaneously; At organic catalysis and Environmental Science and Engineering field very big application potential is arranged.
The invention also discloses and a kind ofly coat one deck at the titanium dioxide powder particle surface and contain the inorganic fluorine compound clad and have the titanium dioxide powder Preparation of catalysts method of highlight catalytic active.It is presoma with titanium dioxide, method by wet chemistry is deposited on the titanium dioxide powder particle surface, with metal fluoride, fluoride-phosphate mixt, fluor-apatite is clad material, and metal fluoride, fluoride-phosphate mixt or the fluor-apatite that is insoluble in water is coated on the titanium dioxide powder particle surface.Preparation process does not change the crystalline phase of presoma titanium dioxide and forms and average grain diameter, this composite catalyst has the crystal structure similar with the titanium dioxide raw material, crystalline phase is formed and average grain diameter, but the catalyst of gained has the ultraviolet catalytic activity higher than original titanium dioxide.
The inventive method can be at the direct coated inorganic fluoride of the titanium dioxide powder particle surface of commodity that are easy to get or artificial preparation, has realized fluorine element immobilized in the titanium dioxide optical catalyst particle surface; The gained catalyst has very high photocatalytic activity, and the fluorinion concentration of stripping is lower than national limitation standard in water simultaneously; At organic catalysis and Environmental Science and Engineering field very big application potential is arranged.Technology of the present invention is simple, and lower to the equipment requirement, raw material is cheap and easy to get, and product has kept the crystal structure and the composition of matrix titanium dioxide, has improved the ultraviolet light photocatalysis activity of titanium dioxide simultaneously.
Described preparation method is specific as follows:
1 one kinds of surfaces of method are coated with the preparation method one of the titanium dioxide optical catalyst of metal fluoride clad, i.e. alkaline process may further comprise the steps:
1) at normal temperatures, presoma titanium dioxide is scattered in a kind of aqueous solution of the metal cation salt as precipitating reagent TiO
2With the mol ratio of this metal ion be 100: 2~100: 40;
2) under vigorous stirring, add fluorine salt aqueous solution, TiO
2With the fluorine ion mol ratio be 100: 4~100: 120;
3) by adding the pH conditioning agent, the pH value that makes reactant liquor is 8~11;
4) under 60 ℃~100 ℃, reacted 2 hours;
5) be cooled to room temperature after, sediment after filtration, water washing and 70 ℃~120 ℃ oven dry down, grind into powder promptly gets the surperficial titanium dioxide optical catalyst that is coated with the fluoride clad.
Above process is expressed as follows (M wherein
N+Be metal ion):
1) at normal temperatures, presoma titanium dioxide is scattered in the aqueous solution of villiaumite TiO
2With the fluorine ion mol ratio be 100: 4~100: 120;
2) by adding the pH conditioning agent, the pH value that makes reactant liquor is 3~5;
3) add a kind of metal cation salt, TiO as precipitating reagent
2With the mol ratio of this metal ion be 100: 2~100: 40, under 60 ℃~100 ℃, reacted 2 hours;
4) be cooled to room temperature after, sediment after filtration, water washing and 70 ℃~120 ℃ oven dry down, grind into powder promptly gets the surperficial titanium dioxide optical catalyst that is coated with the fluoride clad.
Above process is expressed as follows (M wherein
N+Be metal ion):
3 one kinds of surfaces of method are coated with metal fluoride and the phosphate preparation method one of the titanium dioxide optical catalyst of clad altogether, i.e. alkaline process may further comprise the steps:
1) at normal temperatures, presoma titanium dioxide is scattered in a kind of aqueous solution of the metal cation salt as precipitating reagent TiO
2With the mol ratio of this metal ion be 100: 3~100: 20;
2) under vigorous stirring, add villiaumite and phosphate mixed aqueous solution, TiO
2With the fluorine ion mol ratio be 100: 3~100: 57, TiO
2With the phosphate anion mol ratio be 100: 1~100: 8;
3) by adding the pH conditioning agent, the pH value that makes reactant liquor is 8~11;
4) under 60 ℃~100 ℃, reacted 2 hours;
5) be cooled to room temperature after, sediment after filtration, water washing and 70 ℃~120 ℃ oven dry down, grind into powder promptly get the surperficial titanium dioxide optical catalyst that is coated with fluoride and the common clad of phosphate.
4 one kinds of surfaces of method are coated with metal fluoride and the phosphate preparation method two of the titanium dioxide optical catalyst of clad altogether, i.e. acid system may further comprise the steps:
1) at normal temperatures, presoma titanium dioxide is scattered in villiaumite and the phosphate mixed aqueous solution TiO
2With the fluorine ion mol ratio be 100: 3~100: 57, TiO
2With the phosphate anion mol ratio be 100: 1~100: 8;
2) by adding the pH conditioning agent, the pH value that makes reactant liquor is 3~5;
3) add a kind of metal cation salt, TiO as precipitating reagent
2With the mol ratio of this metal ion be 100: 3~100: 20;
4) under 60 ℃~100 ℃, reacted 2 hours;
5) be cooled to room temperature after, sediment after filtration, water washing and 70 ℃~120 ℃ oven dry down, grind into powder promptly get the surperficial titanium dioxide optical catalyst that is coated with fluoride and the common clad of phosphate.
5 one kinds of surfaces of method are coated with the preparation method of the titanium dioxide optical catalyst of fluor-apatite clad, it is characterized in that it may further comprise the steps:
1) under the normal temperature, presoma titanium dioxide is scattered in the aqueous solution as the metal cation salt of precipitating reagent TiO
2With the mol ratio of this metal ion be 100: 2~100: 20;
2) under the condition of boiling, add the mixed aqueous solution that contains fluorine ion and phosphate anion, TiO
2With the phosphate anion mol ratio be 100: 1.2~100: 12, TiO
2With the fluorine ion mol ratio be 100: 0.4~100: 4.
3) by adding the pH conditioning agent, the pH value that makes reactant liquor is 7~10, under 60 ℃~90 ℃, and ageing 1 hour.
4) be cooled to room temperature after, sediment after filtration, washing and 70 ℃~120 ℃ down oven dry, grind into powder promptly gets the surperficial titanium dioxide optical catalyst that contains the fluor-apatite clad.
Reaction equation can be expressed as (with M
N+For bivalent metal ion is an example):
In the above preparation process, selected presoma be the titanium dioxide of commodity or voluntarily the preparation titanium dioxide.
Can be selected from the soluble-salt (as calcium nitrate, lanthanum nitrate etc.) of alkaline-earth metal or lanthanide series metal as the metal ion of precipitating reagent.
Fluoride salt can be any one or two or three the mixing in potassium fluoride, sodium fluoride, the ammonium fluoride etc.
Phosphate can be selected from following any: dipotassium hydrogen phosphate, sodium hydrogen phosphate, diammonium hydrogen phosphate etc., or its mixing of any two or three.
The pH conditioning agent can be any two or three, four kind the mixing of any in dilute solution of sodium hydroxide, ammoniacal liquor weak solution, watery hydrochloric acid or the rare perchloric acid etc. or its.
Catalyst to the evaluation method of organic matter absorption property is: 50mg catalyst and 50ml concentration are 2 of 40ppm, and 4-chlorophenesic acid solution mixes, the lucifuge shaken overnight.Get the 1.5ml reactant liquor, filter, measure the concentration C of chlorophenol in the filtrate with high-efficient liquid phase chromatogram HPLC (Dionex P680) through miillpore filter (0.45 μ m)
eAccording to the change in concentration of chlorophenol before and after the absorption, calculate the adsorbance q of catalyst
eAccording to q
eWith C
eMapping, the absorption property difference of measurement different catalysts.
The evaluation method of photocatalytic activity is: (375W) is outer irradiation source with high-pressure sodium lamp, and radiation dominant wavelength 365nm, catalyst amount are 50mg, is that the phenol solution of 40ppm is mixed the lucifuge shaken overnight with 50ml concentration before the reaction.Illumination reaction carries out in the Pyrex glass container that possesses the cool cycles water leg, and reaction temperature remains on 25 ± 2 ℃.Get the 1.5ml reactant liquor at regular intervals, filter, measure phenol concentration C in the filtrate with HPLC through miillpore filter (0.45 μ m)
T.According to C
tWith the variation relation of light application time, weigh the relative photocatalytic activity of different catalysts.Meanwhile, adopt chromatography of ions (DionexISC90), detect the concentration of stripping fluorine ion in the filtrate.
Embodiment one
Get 1g commodity anatase phase oxidation titanium (AT), being scattered in 100ml concentration is that (mM is 10 to 6mM
-3Mol/L) Ca (NO
3)
2(solution S 1) places magnetic stirrer under the room temperature in the aqueous solution, slowly splashes into the NH that 100mL concentration is 12mM
4The F aqueous solution (solution S 2).By adding 20% weak aqua ammonia, hierarchy of control pH value is about 10.After being added dropwise to complete, water-bath adds hot suspension to 80 ℃, and keeps 2 hours under this temperature.After naturally cooling to room temperature, the suspension ageing is spent the night.After gained precipitated after filtration, washs, 60 ℃ of dryings obtained calcirm-fluoride cladding titanium dioxide catalyst A (seeing A line in Fig. 1~4).TiO wherein
2With the molar ratio of Ca element, F element be 100: 4.8: 9.6.With above-mentioned photocatalytic activity evaluation method, irradiation is after 1 hour under ultraviolet light, and catalyst A and AT Pyrogentisinic Acid's degradation rate is respectively 45.71% and 38.09%.Obviously, under the same conditions, catalyst A has stronger ultraviolet catalytic activity than catalyst A T.
Embodiment two
Get 1g commodity anatase phase oxidation titanium, being scattered in 100ml concentration is the Ca (NO of 5mM
3)
2In the aqueous solution.Boiling under the state, slowly splashing into 100mL 3mM (NH
4)
2HPO
4With 1mM NH
4The mixed solution of F.By adding 20% weak aqua ammonia, hierarchy of control pH value is about 9.After being added dropwise to complete, suspension was 80 ℃ of following ageings 1 hour.After naturally cooling to room temperature, after gained precipitated after filtration, washs, 60 ℃ of dried overnight obtained fluor-apatite cladding titanium dioxide catalyst B (seeing B line in Fig. 1~4).TiO wherein
2With the molar ratio of Ca element, P element, F element be 100: 4.0: 2.4: 0.8.With above-mentioned photocatalytic activity evaluation method, irradiation is after 1 hour under ultraviolet light, and the degradation rate of phenol is 48.70%.
Embodiment three
Experiment condition, step are with embodiment one, with Ca (NO in the solution S 1
3)
2Concentration change 9mM into, solution S 2 is replaced with 2mM (NH
4)
2HPO
4With 12mM NH
4The mixed solution of F makes calcirm-fluoride-calcium phosphate cladding titanium dioxide catalyst C (seeing C curve in Fig. 3~4) altogether.TiO wherein
2With the molar ratio of Ca element, P element, F element be 100: 7.2: 1.6: 9.6, with above-mentioned photocatalytic activity evaluation method, after 1 hour, the degradation rate of phenol is 46.59% under UV-irradiation.
Embodiment four
Get 1g commodity anatase phase oxidation titanium, being scattered in 100ml concentration is the Ca (NO of 3mM
3)
2In the aqueous solution, place magnetic stirrer under the room temperature, slowly splash into the NH that 100mL concentration is 6mM
4The F aqueous solution.By adding 20% weak aqua ammonia, hierarchy of control pH value is about 10.After being added dropwise to complete, water-bath adds hot suspension to 80 ℃, and keeps 2 hours under this temperature.After naturally cooling to room temperature, the suspension ageing is spent the night.After gained precipitated after filtration, washs, 60 ℃ of dryings obtained calcirm-fluoride cladding titanium dioxide catalyst.TiO wherein
2With the molar ratio of Ca element, F element be 100: 2.4: 4.8.With above-mentioned photocatalytic activity evaluation method, irradiation is after 1 hour under ultraviolet light, and the degradation rate of phenol is respectively 42.71%.
Embodiment five
Get 1g commodity anatase phase oxidation titanium, being scattered in 100ml concentration is the Ca (NO of 9mM
3)
2In the aqueous solution, place magnetic stirrer under the room temperature, slowly splash into the NH that 100mL concentration is 18mM
4The F aqueous solution.By adding 20% weak aqua ammonia, hierarchy of control pH value is about 10.After being added dropwise to complete, water-bath adds hot suspension to 80 ℃, and keeps 2 hours under this temperature.After naturally cooling to room temperature, the suspension ageing is spent the night.After gained precipitated after filtration, washs, 60 ℃ of dryings obtained calcirm-fluoride cladding titanium dioxide catalyst.TiO wherein
2With the molar ratio of Ca element, F element be 100: 7.2: 14.4.With above-mentioned photocatalytic activity evaluation method, irradiation is after 1 hour under ultraviolet light, and the degradation rate of phenol is respectively 49.00%.
Embodiment six
Get 1g commodity anatase phase oxidation titanium, being scattered in 100ml concentration is the Ca (NO of 20mM
3)
2In the aqueous solution, place magnetic stirrer under the room temperature, slowly splash into the NH that 100mL concentration is 40mM
4The F aqueous solution.By adding 20% weak aqua ammonia, hierarchy of control pH value is about 10.After being added dropwise to complete, water-bath adds hot suspension to 80 ℃, and keeps 2 hours under this temperature.After naturally cooling to room temperature, the suspension ageing is spent the night.After gained precipitated after filtration, washs, 60 ℃ of dryings obtained calcirm-fluoride cladding titanium dioxide catalyst.TiO wherein
2With the molar ratio of Ca element, F element be 100: 16: 32.With above-mentioned photocatalytic activity evaluation method, irradiation is after 1 hour under ultraviolet light, and the degradation rate of phenol is respectively 42.24%.
Embodiment seven
Get 1g commodity anatase phase oxidation titanium, being scattered in 100ml concentration is the Ca (NO of 50mM
3)
2(solution S 1) places magnetic stirrer under the room temperature in the aqueous solution, slowly splashes into the NH that 100mL concentration is 100mM
4The F aqueous solution (solution S 2).By adding 20% weak aqua ammonia, hierarchy of control pH value is about 10.After being added dropwise to complete, water-bath adds hot suspension to 80 ℃, and keeps 2 hours under this temperature.After naturally cooling to room temperature, the suspension ageing is spent the night.After gained precipitated after filtration, washs, 60 ℃ of dryings obtained calcirm-fluoride cladding titanium dioxide catalyst.TiO wherein
2With the molar ratio of Ca element, F element be 100: 40: 80.With above-mentioned photocatalytic activity evaluation method, irradiation is after 1 hour under ultraviolet light, and the degradation rate of phenol is respectively 31.01%.
Embodiment eight
Experiment condition, step are with embodiment three, with Ca (NO in the solution S 1
3)
2Concentration change 6mM into, solution S 2 is replaced with 2mM (NH
4)
2HPO
4With 6mM NH
4The mixed solution of F makes calcirm-fluoride-calcium phosphate cladding titanium dioxide catalyst C (seeing C curve in Fig. 3 ~ 4) altogether.TiO wherein
2With the molar ratio of Ca element, P element, F element be 100: 4.8: 1.6: 4.8, with above-mentioned photocatalytic activity evaluation method, after 1 hour, the degradation rate of phenol is 44.60% under UV-irradiation.
Embodiment nine
Get 1g commodity anatase phase oxidation titanium, being scattered in 100ml concentration is the Ca (NO of 2.5mM
3)
2In the aqueous solution.Boiling under the state, slowly splashing into 100mL 1.5mM (NH
4)
2HPO
4With 0.5mM NH
4The mixed solution of F.By adding 20% weak aqua ammonia, hierarchy of control pH value is about 9.After being added dropwise to complete, suspension was 80 ℃ of following ageings 1 hour.After naturally cooling to room temperature, after gained precipitated after filtration, washs, 60 ℃ of dried overnight obtained fluor-apatite cladding titanium dioxide catalyst B (seeing B line in Fig. 1 ~ 4).TiO wherein
2With the molar ratio of Ca element, P element, F element be 100: 2.0: 1.2: 0.4.With above-mentioned photocatalytic activity evaluation method, irradiation is after 1 hour under ultraviolet light, and the degradation rate of phenol is 45.88%.
Embodiment ten
Get 1g commodity anatase phase oxidation titanium, being scattered in 100ml concentration is the Ca (NO of 10mM
3)
2In the aqueous solution.Boiling under the state, slowly splashing into 100mL 6mM (NH
4)
2HPO
4With 2mM NH
4The mixed solution of F.By adding 20% weak aqua ammonia, hierarchy of control pH value is about 9.After being added dropwise to complete, suspension was 80 ℃ of following ageings 1 hour.After naturally cooling to room temperature, after gained precipitated after filtration, washs, 60 ℃ of dried overnight obtained fluor-apatite cladding titanium dioxide catalyst B (seeing B line in Fig. 1 ~ 4).TiO wherein
2With the molar ratio of Ca element, P element, F element be 100: 8.0: 4.8: 1.6.With above-mentioned photocatalytic activity evaluation method, irradiation is after 1 hour under ultraviolet light, and the degradation rate of phenol is 48.30%.
Embodiment 11
Get 1g commodity anatase phase oxidation titanium, being scattered in 100ml concentration is the Ca (NO of 20mM
3)
2In the aqueous solution.Boiling under the state, slowly splashing into 100mL 12mM (NH
4)
2HPO
4With 4mM NH
4The mixed solution of F.By adding 20% weak aqua ammonia, hierarchy of control pH value is about 9.After being added dropwise to complete, suspension was 80 ℃ of following ageings 1 hour.After naturally cooling to room temperature, after gained precipitated after filtration, washs, 60 ℃ of dried overnight obtained fluor-apatite cladding titanium dioxide catalyst B (seeing B line in Fig. 1 ~ 4).TiO wherein
2With the molar ratio of Ca element, P element, F element be 100: 16.0: 9.6: 3.2.With above-mentioned photocatalytic activity evaluation method, irradiation is after 1 hour under ultraviolet light, and the degradation rate of phenol is 42.70%.
Claims (10)
1. titanium dioxide optical catalyst that the surface is coated with coating layer, it is characterized in that: it comprises the titanium dioxide powder particle, and described titanium dioxide powder particle is provided with metal fluoride clad, metal fluoride phosphate clad or fluor-apatite clad altogether outward.
2. a surface is coated with the preparation method one of the titanium dioxide optical catalyst of metal fluoride clad, it is characterized in that it may further comprise the steps:
1) at normal temperatures, presoma titanium dioxide is scattered in a kind of aqueous solution of the metal cation salt as precipitating reagent TiO
2With the mol ratio of this metal ion be 100: 2~100: 40;
2) under vigorous stirring, add fluorine salt aqueous solution, TiO
2With the fluorine ion mol ratio be 100: 4~100: 120;
3) by adding the pH conditioning agent, the pH value that makes reactant liquor is 8~11;
4) under 60 ℃~100 ℃, reacted 2 hours;
5) be cooled to room temperature after, sediment after filtration, water washing and 70 ℃~120 ℃ oven dry down, grind into powder promptly gets the surperficial titanium dioxide optical catalyst that is coated with the metal fluoride clad.
3. a surface is coated with the preparation method two of the titanium dioxide optical catalyst of metal fluoride clad, it is characterized in that it may further comprise the steps:
1) at normal temperatures, presoma titanium dioxide is scattered in the aqueous solution of villiaumite TiO
2With the fluorine ion mol ratio be 100: 4~100: 120;
2) by adding the pH conditioning agent, the pH value that makes reactant liquor is 3~5;
3) add a kind of metal cation salt, TiO as precipitating reagent
2With the mol ratio of this metal ion be 100: 2~100: 40, under 60 ℃~100 ℃, reacted 2 hours;
4) be cooled to room temperature after, sediment after filtration, water washing and 70 ℃~120 ℃ oven dry down, grind into powder promptly gets the surperficial titanium dioxide optical catalyst that is coated with the metal fluoride clad.
4. a surface is coated with metal fluoride and the phosphate preparation method one of the titanium dioxide optical catalyst of clad altogether, it is characterized in that it may further comprise the steps:
1) at normal temperatures, presoma titanium dioxide is scattered in a kind of aqueous solution of the metal cation salt as precipitating reagent TiO
2With the mol ratio of this metal ion be 100: 3~100: 20;
2) under vigorous stirring, add villiaumite and phosphate mixed aqueous solution, TiO
2With the fluorine ion mol ratio be 100: 3~100: 57, TiO
2With the phosphate anion mol ratio be 100: 1~100: 8;
3) by adding the pH conditioning agent, the pH value that makes reactant liquor is 8~11;
4) under 60 ℃~100 ℃, reacted 2 hours;
5) be cooled to room temperature after, sediment after filtration, water washing and 70 ℃~120 ℃ oven dry down, grind into powder promptly get the surperficial titanium dioxide optical catalyst that is coated with fluoride and the common clad of phosphate.
5. a surface is coated with metal fluoride and the phosphate preparation method two of the titanium dioxide optical catalyst of clad altogether, it is characterized in that it may further comprise the steps:
1) at normal temperatures, presoma titanium dioxide is scattered in villiaumite and the phosphate mixed aqueous solution TiO
2With the fluorine ion mol ratio be 100: 3~100: 57, TiO
2With the phosphate anion mol ratio be 100: 1~100: 8;
2) by adding the pH conditioning agent, the pH value that makes reactant liquor is 3~5;
3) adding is as the metal cation salt of precipitating reagent, TiO
2With the mol ratio of this metal ion be 100: 3~100: 20;
4) under 60 ℃~100 ℃, reacted 2 hours;
5) be cooled to room temperature after, sediment after filtration, water washing and 70 ℃~120 ℃ oven dry down, grind into powder promptly get the surperficial titanium dioxide optical catalyst that is coated with fluoride and the common clad of phosphate.
6. a surface is coated with the preparation method of the titanium dioxide optical catalyst of fluor-apatite clad, it is characterized in that it may further comprise the steps:
1) under the normal temperature, presoma titanium dioxide is scattered in the aqueous solution as the metal cation salt of precipitating reagent TiO
2With the mol ratio of this metal ion be 100: 2~100: 20;
2) under the condition of boiling, add the mixed aqueous solution that contains fluorine ion and phosphate anion, TiO
2With the phosphate anion mol ratio be 100: 1.2~100: 12, TiO
2With the fluorine ion mol ratio be 100: 0.4~100: 4;
3) by adding the pH conditioning agent, the pH value that makes reactant liquor is 7~10, under 60 ℃~90 ℃, and ageing 1 hour;
4) be cooled to room temperature after, sediment after filtration, washing and 70 ℃~120 ℃ down oven dry, grind into powder promptly gets the surperficial titanium dioxide optical catalyst that contains the fluor-apatite clad.
7. according to the method for the surperficial titanium dioxide optical catalyst that is coated with coating layer of the described preparation of claim 2~6, it is characterized in that described metal cation salt as precipitating reagent is selected from the soluble-salt of alkaline-earth metal or lanthanide series metal.
8. the method for the titanium dioxide optical catalyst that is coated with coating layer according to the described preparation surface of claim 2~6 is characterized in that described fluoride can be any one or two or three the mixing in sodium fluoride, potassium fluoride, the ammonium fluoride.
9. according to the method for claim 4,5, the surperficial titanium dioxide optical catalyst that is coated with coating layer of 6 described preparations, it is characterized in that described phosphate can be dipotassium hydrogen phosphate, sodium hydrogen phosphate or diammonium hydrogen phosphate or its mixing of any two or three.
10. the method for the titanium dioxide optical catalyst that is coated with coating layer according to the described preparation surface of claim 2~6 is characterized in that described pH conditioning agent can be the mixing of dilute solution of sodium hydroxide, ammoniacal liquor weak solution, watery hydrochloric acid or rare perchloric acid or its any two or three or four kind.
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