CN103182303B - Nano titanium oxide, the preparation method and its usage of thulium doping - Google Patents
Nano titanium oxide, the preparation method and its usage of thulium doping Download PDFInfo
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 85
- 229910052775 Thulium Inorganic materials 0.000 title claims abstract description 44
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 title claims abstract description 42
- FRNOGLGSGLTDKL-UHFFFAOYSA-N thulium atom Chemical compound [Tm] FRNOGLGSGLTDKL-UHFFFAOYSA-N 0.000 title claims abstract description 35
- 238000002360 preparation method Methods 0.000 title abstract description 8
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims abstract description 45
- 229910001404 rare earth metal oxide Inorganic materials 0.000 claims abstract description 32
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims abstract description 27
- 229910000420 cerium oxide Inorganic materials 0.000 claims abstract description 21
- PLDDOISOJJCEMH-UHFFFAOYSA-N neodymium(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Nd+3].[Nd+3] PLDDOISOJJCEMH-UHFFFAOYSA-N 0.000 claims abstract description 21
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000004408 titanium dioxide Substances 0.000 claims abstract description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000007788 liquid Substances 0.000 claims abstract description 15
- 239000001488 sodium phosphate Substances 0.000 claims abstract description 15
- 229910000162 sodium phosphate Inorganic materials 0.000 claims abstract description 15
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 claims abstract description 15
- 239000003513 alkali Substances 0.000 claims abstract description 14
- 238000001035 drying Methods 0.000 claims abstract description 6
- 238000001914 filtration Methods 0.000 claims abstract description 6
- 238000000034 method Methods 0.000 claims description 18
- 239000002245 particle Substances 0.000 claims description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 4
- 150000008044 alkali metal hydroxides Chemical class 0.000 claims description 3
- 229910001860 alkaline earth metal hydroxide Inorganic materials 0.000 claims description 2
- 229910021529 ammonia Inorganic materials 0.000 claims description 2
- 238000010521 absorption reaction Methods 0.000 abstract description 9
- 239000011248 coating agent Substances 0.000 abstract description 7
- 238000000576 coating method Methods 0.000 abstract description 7
- 239000003054 catalyst Substances 0.000 abstract description 5
- 238000002425 crystallisation Methods 0.000 abstract description 5
- 230000008025 crystallization Effects 0.000 abstract description 5
- 238000005265 energy consumption Methods 0.000 abstract description 4
- 230000000505 pernicious effect Effects 0.000 abstract description 4
- 238000013033 photocatalytic degradation reaction Methods 0.000 abstract description 3
- 239000002105 nanoparticle Substances 0.000 abstract 1
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 27
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 24
- 238000003756 stirring Methods 0.000 description 20
- 238000006243 chemical reaction Methods 0.000 description 18
- 238000001246 colloidal dispersion Methods 0.000 description 15
- 239000007787 solid Substances 0.000 description 15
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 12
- 235000011121 sodium hydroxide Nutrition 0.000 description 11
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 9
- 239000000839 emulsion Substances 0.000 description 8
- 239000000203 mixture Substances 0.000 description 7
- 239000007864 aqueous solution Substances 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 239000013078 crystal Substances 0.000 description 4
- 229910052746 lanthanum Inorganic materials 0.000 description 4
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical group [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 4
- 229910052684 Cerium Inorganic materials 0.000 description 3
- 229910052688 Gadolinium Inorganic materials 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 3
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 3
- 238000005034 decoration Methods 0.000 description 3
- UIWYJDYFSGRHKR-UHFFFAOYSA-N gadolinium atom Chemical group [Gd] UIWYJDYFSGRHKR-UHFFFAOYSA-N 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 230000001699 photocatalysis Effects 0.000 description 3
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 2
- 229910052693 Europium Inorganic materials 0.000 description 2
- 229910052779 Neodymium Inorganic materials 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- 238000002835 absorbance Methods 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- OGPBJKLSAFTDLK-UHFFFAOYSA-N europium atom Chemical compound [Eu] OGPBJKLSAFTDLK-UHFFFAOYSA-N 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 description 2
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 description 2
- 239000011941 photocatalyst Substances 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 238000000967 suction filtration Methods 0.000 description 2
- 206010013786 Dry skin Diseases 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical group Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- MKYBYDHXWVHEJW-UHFFFAOYSA-N N-[1-oxo-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propan-2-yl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(C(C)NC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 MKYBYDHXWVHEJW-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 229910052777 Praseodymium Inorganic materials 0.000 description 1
- 208000031320 Teratogenesis Diseases 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 150000001555 benzenes Chemical class 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 230000000711 cancerogenic effect Effects 0.000 description 1
- 231100000315 carcinogenic Toxicity 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 229910001940 europium oxide Inorganic materials 0.000 description 1
- AEBZCFFCDTZXHP-UHFFFAOYSA-N europium(3+);oxygen(2-) Chemical class [O-2].[O-2].[O-2].[Eu+3].[Eu+3] AEBZCFFCDTZXHP-UHFFFAOYSA-N 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 238000002703 mutagenesis Methods 0.000 description 1
- 231100000350 mutagenesis Toxicity 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- PUDIUYLPXJFUGB-UHFFFAOYSA-N praseodymium atom Chemical compound [Pr] PUDIUYLPXJFUGB-UHFFFAOYSA-N 0.000 description 1
- 238000004451 qualitative analysis Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000004659 sterilization and disinfection Methods 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000003505 terpenes Chemical class 0.000 description 1
- 235000007586 terpenes Nutrition 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 1
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- Inorganic Compounds Of Heavy Metals (AREA)
- Catalysts (AREA)
- Cosmetics (AREA)
Abstract
The present invention relates to the nano titanium oxide of thulium doping, wherein rare-earth oxide is 0.1-12 % by weight based on the percetage by weight of titanium dioxide, rare-earth oxide to be weight ratio be 0.1: 1-5: 1 cerium oxide and neodymia.The invention still further relates to its preparation method, comprising: a) rare-earth oxide and titanium tetrachloride that meet described percetage by weight and weight ratio are added to the water; B) citric acid/dibastic sodium phosphate cushioning liquid is added; C) with alkali, pH value is adjusted to 5-6; D) react under the pressure of the temperature of 100-200 DEG C and 0.2-0.8MPa; And e) filtration and drying.The invention still further relates to its purposes as photochemical catalyst in coating.Described titanium dioxide nanoparticle is Detitanium-ore-type and crystallization degree is good; Its absorption band is to the obvious red shift in visible ray direction; Can pernicious gas effectively in photocatalytic degradation environment; Its preparation method is simple and convenient and energy consumption is low.
Description
Technical field
The present invention relates to the nano titanium oxide of thulium doping, prepare the method for nano titanium oxide of described thulium doping, and the nano titanium oxide of described thulium doping in coating as the purposes of photochemical catalyst.
Background technology
Along with the raising of people's living standard, house fitting becomes fashion gradually, and luxurious interior decoration also becomes the target that people pursue.House decoration can build comfortable, graceful, elegant living environment, and beautifies the life of people.But people are while enjoying everything fine, and the pollution that house decoration causes living environment and these polluters are also constantly strengthening the adverse effect that human body brings.At present, the quality of room air has caused the common concern of various circles of society.
Investigation shows organic pollution materials in the room of recently fitting up and reaches more than 500 kinds, comprise aldehydes, benzene class, ethers, ester class, alcohols, ketone, terpenes etc., wherein have 20 many kinds of substances to have stronger carcinogenic, teratogenesis and mutagenesis to human body, especially formaldehyde, benzene, toluene, ethylbenzene, dimethylbenzene etc. are larger to the harm of human body.
Titanium dioxide receives the increasingly extensive concern of people as photochemical catalyst.Titanium dioxide is as a kind of semiconductor functional material, and its photocatalytic activity determines primarily of the crystal structure of self.But, bands of a spectrum response range and the catalytic efficiency of titanium dioxide can be improved by doping vario-property.
Chinese invention patent application CN1631521A discloses and prepares titanium dioxide optical catalyst by coprecipitation-calcination method, wherein in coprecipitation reaction process, by the nitrate of thulium with thulium: the weight ratio of titanium dioxide=0.5-1.5% adds in titanium tetrachloride aqueous solution, and wherein thulium is selected from lanthanum, cerium, praseodymium, neodymium.
Chinese invention patent application CN1654335A discloses the preparation method of visible light photoactivated anatase type TiO 2 sol, wherein titania-dopedly realizes by using lanthanum, cerium, neodymium, the salt of europium or its mixture.
Chinese invention patent application CN102059110A discloses the preparation method of the nano titanium dioxide photocatalyst of two kinds of thulium codopes, and wherein said thulium is gadolinium and lanthanum, gadolinium and yttrium, lanthanum and cerium or gadolinium and europium.
If be doped in titanium dioxide by two kinds of different thuliums simultaneously, when selected two kinds of thuliums are suitable and the two proportioning is suitable, they will improve the photocatalytic activity of titanium dioxide jointly.
Summary of the invention
In view of above-mentioned prior art situation, present inventor has carried out research extensively and profoundly in nano titanium oxide field, to obtaining the nano titanium oxide that a kind of photocatalytic activity significantly improves.Found that cerium oxide by by weight ratio being 0.1: 1-5: 1 and neodymia are doped to the nano titanium oxide that can obtain in titanium dioxide and meet above-mentioned requirements.Inventor completes the present invention based on above-mentioned discovery just.
The object of this invention is to provide a kind of nano titanium oxide, its cerium oxide doped with 0.1-12 % by weight and neodymia, the weight ratio of cerium oxide and neodymia is 0.1: 1-5: 1.
Another object of the present invention is to provide a kind of method preparing above-mentioned nano titanium oxide.
Another object of the present invention is to provide the purposes of above-mentioned nano titanium oxide.
One aspect of the present invention provides the nano titanium oxide of a kind of thulium doping, wherein rare-earth oxide is 0.1-12 % by weight based on the percetage by weight of titanium dioxide, rare-earth oxide is cerium oxide and neodymia, and the weight ratio of cerium oxide and neodymia is 0.1: 1-5: 1.
The present invention provides a kind of method preparing the nano titanium oxide of above-mentioned thulium doping on the other hand, said method comprising the steps of:
A) rare-earth oxide and titanium tetrachloride that meet described percetage by weight and weight ratio are added to the water;
B) citric acid/dibastic sodium phosphate cushioning liquid is added;
C) with alkali, pH value is adjusted to 5-6;
D) react under the pressure of the temperature of 100-200 DEG C and 0.2-0.8MPa; With
E) filtration and drying.
Further aspect of the present invention provide above-mentioned thulium doping nano titanium oxide in coating as the purposes of photochemical catalyst.
The nano titanium oxide of thulium doping of the present invention is Detitanium-ore-type, and crystallization degree is good; Its absorption band is to the obvious red shift in visible ray direction; Can pernicious gas effectively in photocatalytic degradation environment; Its preparation method is simple and convenient and energy consumption is low.
These and other purposes, features and advantages of the present invention, after considering the present invention in conjunction with following accompanying drawing entirety, will be easy to as those of ordinary skill is understood.
Accompanying drawing explanation
Fig. 1 is the transmission electron microscope photo of the colloidal dispersion of the embodiment of the present invention 1.
Fig. 2 is the X-ray diffractogram of the nano titanium oxide of the thulium doping of the embodiment of the present invention 1.
Fig. 3 shows the absorbance of nano titanium oxide in 200-1200nm wave-length coverage of the thulium doping of the embodiment of the present invention 1.
Detailed description of the invention
The nano titanium oxide of thulium doping of the present invention is made up of titanium dioxide and the rare-earth oxide be entrained in wherein.
Absorption band red shift gradually along with the increase of thulium doping of the nano titanium oxide of thulium doping, it obviously increases the absorptivity of visible ray.But along with the increase of thulium doping, the anatase peak-to-peak signal of nano titanium oxide in XRD of thulium doping weakens gradually, and this illustrates that the doping of thulium inhibits the growth of anatase crystal to a certain extent.
Therefore, in the nano titanium oxide of thulium doping of the present invention, rare-earth oxide is 0.1-12 % by weight based on the percetage by weight of titanium dioxide, preferred 1-8 % by weight, more preferably 2-5 % by weight.
When rare-earth oxide based on titanium dioxide percetage by weight lower than 0.1 % by weight, absorption band is not obvious to the red shift of visible ray; When rare-earth oxide based on titanium dioxide percetage by weight higher than 12 % by weight, the growth of anatase crystal receives and suppresses largely, and its respective peaks signal in XRD is more weak, and cost obviously increases.
In the nano titanium oxide of thulium of the present invention doping, rare-earth oxide is the mixture of cerium oxide and neodymia, and wherein the weight ratio of cerium oxide and neodymia is 0.1: 1-5: 1, preferably 0.3: 1-3: 1, more preferably 0.5: 1-2: 1.
When the weight ratio of cerium oxide and neodymia is less than 0.1: 1, the hole of generation is inadequate, and then causes absorption band not obvious to the red shift of visible ray; When the weight ratio of cerium oxide and neodymia is greater than 5: 1, nano titanium dioxide crystal form will be a greater impact to the transformation of Detitanium-ore-type.
The feature of the nano titanium oxide of thulium doping of the present invention is also that it is the form of solid solution, and wherein thulium enters in the lattice of titanium dioxide.
The particle diameter of the nano titanium oxide of thulium doping of the present invention is 10-80nm, preferred 20-50nm.
The nano titanium oxide of thulium doping of the present invention is Detitanium-ore-type, and crystallization degree is good.
Compared with the nano titanium oxide not having to adulterate, the absorption band of the nano titanium oxide of thulium doping of the present invention is to the red shift of visible ray direction, and it obviously increases the absorptivity of visible ray.
The nano titanium oxide of thulium doping of the present invention is prepared by following method:
A) rare-earth oxide and titanium tetrachloride that meet above-mentioned percetage by weight and weight ratio are added to the water;
B) citric acid/dibastic sodium phosphate cushioning liquid is added;
C) with alkali, pH value is adjusted to 5-6; With
D) react under the pressure of the temperature of 100-200 DEG C and 0.2-0.8MPa; With
E) filtration and drying.
Step a)
Particularly, step a) is performed as follows usually: first add in titanium tetrachloride by the rare-earth oxide meeting above-mentioned percetage by weight, is finally added to the water by the mixture of gained rare-earth oxide and titanium tetrachloride.
Above-mentioned percetage by weight specifically refers to that the titanium dioxide in the nano titanium oxide that rare-earth oxide adulterates based on thulium of the present invention is 0.1-12 % by weight, preferred 1-8 % by weight, more preferably 2-5 % by weight.
Rare-earth oxide used is preferably the mixture of cerium oxide and neodymia.
For this reason, before rare-earth oxide is added in titanium tetrachloride, need to meet cerium oxide and the neodymia mixing of above-mentioned weight ratio.
Above-mentioned weight ratio specifically refers to that the weight ratio of cerium oxide and neodymia is 0.1: 1-5: 1, preferably 0.3: 1-3: 1, more preferably 0.5: 1-2: 1.
Rare-earth oxide carried out usually with mixing of titanium tetrachloride in closed reaction vessel.If needed, described mixing also can be carried out in inert gas is as nitrogen atmosphere.
Usually at room temperature the mixture of gained rare-earth oxide and titanium tetrachloride is added to the water, stirs simultaneously.It is suitable that, the weight ratio of titanium tetrachloride and water is 1: 8-1: 15.Control adds the speed of the mixture of rare-earth oxide and titanium tetrachloride thus the hydrolysis of titanium tetrachloride and water is leniently carried out to controllably.After adding, continue to stir to make titanium tetrachloride continue hydrolysis 30-90 minute.
As alternative, also can successively the rare-earth oxide and titanium tetrachloride that meet above-mentioned percetage by weight and weight ratio be added to the water.
As alternative, also can the rare-earth oxide and titanium tetrachloride that meet above-mentioned percetage by weight and weight ratio be added to the water simultaneously.
In described two kinds of alternative, concrete operations are as just wherein first mixed rare-earth oxide with titanium tetrachloride, described in the embodiment be then added to the water by gained mixture above.Or, can suitably change described concrete operations according to actual needs.
Step b)
In step b) in, citric acid/dibastic sodium phosphate cushioning liquid (aqueous solution) is added step a) in gained mixed system.The pH value of citric acid/dibastic sodium phosphate cushioning liquid is 5-6 suitably, such as about 5.5.The consumption of citric acid/dibastic sodium phosphate cushioning liquid is 0.6-2 times of titanium tetrachloride weight.
Step c)
In this step, alkali is utilized by step b) pH value of gained mixed system is adjusted to 5-6.Alkali used can be alkali metal hydroxide, alkaline earth metal hydroxide or ammonia, preferred alkali metal hydroxide, especially NaOH.Alkali can solid pure material form use, such as use solid sodium hydroxide.Now, usually add the alkali of described solid form in batches, such as, under stirring, add the alkali of 4/9,3/9 and 2/9 aequum successively.Alkali also can use in form of an aqueous solutions, such as, use sodium hydrate aqueous solution.Now, usually add the alkali of described aqueous solution form with the concentration gradient of successively decreasing in batches, such as, under stirring, add the alkali of 6M, 4M and 2M successively.Those skilled in the art can determine the consumption of alkali easily according to required target ph.
Steps d)
In this step, step c is made) reaction under the pressure of the temperature of 100-200 DEG C and 0.2-0.8MPa of gained mixed system forms colloidal dispersion.
Reaction temperature is preferably 150-180 DEG C.Reaction pressure is preferably 0.4-0.6MPa.When reaction temperature lower than 100 DEG C or reaction pressure lower than 0.2MPa, the amount of the nano titanium oxide of Detitanium-ore-type thulium doping is inadequate; Meanwhile, usually should avoid reaction temperature higher than 200 DEG C or reaction pressure higher than 0.8MPa, because now the energy consumption of reaction system and danger all unnecessarily increase.
Described reaction is carried out in the closed container of high temperature resistant and high pressure, such as, carry out in a kettle..
Select to make step c to the reaction time) hydroxide in gained mixed system is converted into corresponding oxide as much as possible.In gained colloidal dispersion, the nano titanium oxide adulterated as the thulium of solids is more than at least 80 % by weight, preferred more than at least 85 % by weight, more preferably more than at least 90 % by weight, such as 91 % by weight or 92 % by weight, described percetage by weight is in each case all based on the gross weight of the solids be present in continuous aqueous phase.Generally speaking, the reaction time is generally 1-3 hour.
Step e)
In this step, by steps d) gained colloidal dispersion filters and the dry nano titanium oxide obtaining thulium of the present invention doping.
After filtration is as suction filtration and before drying, can optionally wash to remove hydrochloride attached thereto as much as possible to filtration gained solid, but this be optional.Dry usually below 100 DEG C, such as, carry out at the temperature of 55-75 DEG C.
The nano titanium oxide of thulium doping of the present invention is suitable for photocatalyst because of the obvious red shift of its absorption band, and the pernicious gas that can effectively degrade in environment is as formaldehyde and toluene.
For this reason, the nano titanium oxide that thulium of the present invention can be adulterated is direct or add in existing coating after disperseing again, such as, add in commercial coating.Or, also colloidal dispersion according to the present invention directly can be added in existing coating.The nm TiO 2-base of thulium doping is 30-50 % by weight in the gross weight of existing coating.
Nano titanium oxide of thulium doping of the present invention and preparation method thereof has following advantage:
1. particle diameter is 10-80nm;
2. be Detitanium-ore-type, and crystallization degree is good;
3. its absorption band is to the obvious red shift in visible ray direction;
4. can pernicious gas more effectively in photocatalytic degradation environment as toluene and formaldehyde; With
5. by preparing comprising the method for reacting under the pressure of the temperature of 100-200 DEG C and 0.2-0.8MPa, described method is simple and convenient, avoids the calcining step of high energy consumption and therefore high cost.
Embodiment
Hereafter by reference example and accompanying drawing, the present invention is specifically described, but described embodiment does not form any restriction to the scope of the invention.
Transmission electron microscope: company of NEC, JEM-2100 type; Ultraviolet/visible light spectrophotometer: HITACHI, U-3010 type; X-ray diffractometer: Japanese Shimadzu, 7000S type.
Embodiment 1
500 grams of rare-earth oxides (weight ratio of cerium oxide and neodymia is 0.8: 1) are added in 40kg titanium tetrachloride, stirs 1 hour; Added in 400kg water, stirred 40 minutes; Add citric acid/dibastic sodium phosphate cushioning liquid 40kg that pH value is 5.5 wherein; By the pH value to 5.2 of sodium hydrate solid regulation system; 20kg gained mixed system is added in reactor, and reacts 60 minutes under 155 DEG C of conditions with 0.44MPa; A part is reacted gained colloidal dispersion (15kg) to add in the benzene emulsion (Nantong Shengda Chemical Co., Ltd., S-01) of 25kg, stir.
Fig. 1 shows the transmission electron microscope picture of described colloidal dispersion, and it shows that the particle diameter of the nano titanium oxide of the thulium doping wherein existed as solids is 20-50nm.
By described for part colloidal dispersion suction filtration, washing, 65 DEG C of dryings 10 hours, grinding obtained the nano titanium oxide fine particle of thulium doping, and its X-ray diffractogram and the absorbance in 200-1200nm wave-length coverage are respectively as shown in Figures 2 and 3.Fig. 2 shows that it is Detitanium-ore-type, and crystallization degree is good.Fig. 3 shows its absorption band obviously to the red shift of visible ray direction.
Embodiment 2
1000 grams of rare-earth oxides (weight ratio of cerium oxide and neodymia is 1: 1) are added in 40kg titanium tetrachloride, stirs 1 hour; Added in 400kg water, stirred 45 minutes; Add citric acid/dibastic sodium phosphate cushioning liquid 40kg that pH value is 5.5 wherein; By the pH value to 5.4 of sodium hydrate solid regulation system; 20kg gained mixed system is added in reactor, and reacts 65 minutes under 160 DEG C of conditions with 0.48MPa; Reaction gained colloidal dispersion is added in the benzene emulsion of 35kg, stirs.
Embodiment 3
1500 grams of rare-earth oxides (weight ratio of cerium oxide and neodymia is 1.2: 1) are added in 40kg titanium tetrachloride, stirs 1 hour; Added in 320kg water, stirred 50 minutes; Add citric acid/dibastic sodium phosphate cushioning liquid 40kg that pH value is 5.5 wherein; By the pH value to 5.6 of sodium hydrate solid regulation system; 20kg gained mixed system is added in reactor, and reacts 70 minutes under 175 DEG C of conditions with 0.52MPa; Reaction gained colloidal dispersion is added in the benzene emulsion of 40kg, stirs.
Embodiment 4
2000 grams of rare-earth oxides (weight ratio of cerium oxide and neodymia is 1.4: 1) are added in 40kg titanium tetrachloride, stirs 1 hour; Added in 600kg water, stirred 55 minutes; Add citric acid/dibastic sodium phosphate cushioning liquid 40kg that pH value is 5.5 wherein; By the pH value to 5.8 of sodium hydrate solid regulation system; 20kg gained mixed system is added in reactor, and reacts 75 minutes under 170 DEG C of conditions with 0.56MPa; Reaction gained colloidal dispersion is added in the benzene emulsion of 45kg, stirs.
Comparative example 1
40kg titanium tetrachloride is added in 400kg water, stir 40 minutes; Add citric acid/dibastic sodium phosphate cushioning liquid 40kg that pH value is 5.5 wherein; By the pH value to 5.2 of sodium hydrate solid regulation system; 20kg gained mixed system is added in reactor, and reacts 60 minutes under 165 DEG C of conditions with 0.44MPa; Reaction gained colloidal dispersion is added in the benzene emulsion of 25kg, stirs.
Comparative example 2
1000 grams of lanthanas are added in 40kg titanium tetrachloride, stirs 1 hour; Added in 400kg water, stirred 45 minutes; Add citric acid/dibastic sodium phosphate cushioning liquid 40kg that pH value is 5.5 wherein; By the pH value to 5.2 of sodium hydrate solid regulation system; 20kg gained mixed system is added in reactor, and reacts 60 minutes under 165 DEG C of conditions with 0.46MPa; Reaction gained colloidal dispersion is added in the benzene emulsion of 25kg, stirs.
Comparative example 3
1500 grams of yittrium oxide are added in 40kg titanium tetrachloride, stirs 1 hour; Added in 400kg water, stirred 50 minutes; Add citric acid/dibastic sodium phosphate cushioning liquid 40kg that pH value is 5.5 wherein; By the pH value to 5.2 of sodium hydrate solid regulation system; 20kg gained mixed system is added in reactor, and reacts 60 minutes under 170 DEG C of conditions with 0.52MPa; Reaction gained colloidal dispersion is added in the benzene emulsion of 25kg, stirs.
Comparative example 4
2000 grams of europium oxides are added in 40kg titanium tetrachloride, stirs 1 hour; Added in 400kg water, stirred 55 minutes; Add citric acid/dibastic sodium phosphate cushioning liquid 40kg that pH value is 5.5 wherein; By the pH value to 5.2 of sodium hydrate solid regulation system; 20kg gained mixed system is added in reactor, and reacts 60 minutes under 175 DEG C of conditions with 0.58MPa; Reaction gained colloidal dispersion is added in the benzene emulsion of 25kg, stirs.
Performance test
Final products described in embodiment 1-4 and comparative example 1-4 carry out qualitative analysis according to " disinfection technology standard " (version in 2002) to its toxicity by Institute for Environment Hygiene and Health Related Product Safety, China CDC; Detected with regard to its degradation efficiency to toluene and formaldehyde according to JC/T1074-2008 by Chinese building material test center.Acquired results is as shown in the table.
Claims (9)
1. prepare the method for the nano titanium oxide of thulium doping for one kind, wherein rare-earth oxide is 0.1-12 % by weight based on the percetage by weight of titanium dioxide, rare-earth oxide is cerium oxide and neodymia, the weight ratio of cerium oxide and neodymia is 0.1:1-5:1, the particle diameter of the nano titanium oxide of thulium doping is 10-80nm, said method comprising the steps of:
A) rare-earth oxide and titanium tetrachloride that meet described percetage by weight and weight ratio are added to the water;
B) citric acid/dibastic sodium phosphate cushioning liquid is added;
C) with alkali, pH value is adjusted to 5-6;
D) react under the pressure of the temperature of 100-200 DEG C and 0.2-0.8MPa; With
E) filtration and drying.
2. the method for claim 1, wherein rare-earth oxide is 1-8 % by weight based on the percetage by weight of titanium dioxide.
3. method as claimed in claim 2, wherein rare-earth oxide is 2-5 % by weight based on the percetage by weight of titanium dioxide.
4. the method for claim 1, wherein the weight ratio of cerium oxide and neodymia is 0.3:1-3:1.
5. method as claimed in claim 4, wherein the weight ratio of cerium oxide and neodymia is 0.5:1-2:1.
6. the method for claim 1, the particle diameter of the nano titanium oxide of described thulium doping is 20-50nm.
7. the method according to any one of claim 1-6, wherein steps d) carry out under the pressure of the temperature of 150-180 DEG C and 0.4-0.6MPa.
8. the method according to any one of claim 1-6, wherein the weight ratio of titanium tetrachloride and water is 1:8-1:15.
9. the method according to any one of claim 1-6, wherein alkali used is alkali metal hydroxide, alkaline earth metal hydroxide or ammonia.
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| CN105688886A (en) * | 2016-03-07 | 2016-06-22 | 山东源根化学技术研发有限公司 | Preparing method of water-soluble visible-light response photocatalysis degradation agent |
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