CN103182303A - Rare earth metal doped nano titanium dioxide and preparation method and application thereof - Google Patents
Rare earth metal doped nano titanium dioxide and preparation method and application thereof Download PDFInfo
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- CN103182303A CN103182303A CN2011104591717A CN201110459171A CN103182303A CN 103182303 A CN103182303 A CN 103182303A CN 2011104591717 A CN2011104591717 A CN 2011104591717A CN 201110459171 A CN201110459171 A CN 201110459171A CN 103182303 A CN103182303 A CN 103182303A
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- nano titanium
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- thulium
- titanium dioxide
- rare earth
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- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 title abstract description 9
- 238000002360 preparation method Methods 0.000 title abstract description 8
- 229910052761 rare earth metal Inorganic materials 0.000 title abstract 9
- 150000002910 rare earth metals Chemical class 0.000 title abstract 9
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 85
- 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 48
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims abstract description 29
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 22
- 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 20
- 229910000420 cerium oxide Inorganic materials 0.000 claims abstract description 19
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000004408 titanium dioxide Substances 0.000 claims abstract description 17
- 239000003513 alkali Substances 0.000 claims abstract description 16
- 239000011248 coating agent Substances 0.000 claims abstract description 8
- 238000000576 coating method Methods 0.000 claims abstract description 8
- 238000001914 filtration Methods 0.000 claims abstract description 7
- 239000003054 catalyst Substances 0.000 claims abstract description 6
- 239000002245 particle Substances 0.000 claims abstract description 6
- 229910052775 Thulium Inorganic materials 0.000 claims description 49
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 47
- 229910001404 rare earth metal oxide Inorganic materials 0.000 claims description 28
- FRNOGLGSGLTDKL-UHFFFAOYSA-N thulium atom Chemical compound [Tm] FRNOGLGSGLTDKL-UHFFFAOYSA-N 0.000 claims description 19
- 239000007788 liquid Substances 0.000 claims description 15
- 239000001488 sodium phosphate Substances 0.000 claims description 15
- 229910000162 sodium phosphate Inorganic materials 0.000 claims description 15
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 12
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 6
- 150000008044 alkali metal hydroxides Chemical class 0.000 claims description 4
- 229910001860 alkaline earth metal hydroxide Inorganic materials 0.000 claims description 3
- 229910021529 ammonia Inorganic materials 0.000 claims description 3
- 238000006243 chemical reaction Methods 0.000 abstract description 26
- 238000010521 absorption reaction Methods 0.000 abstract description 9
- 238000002425 crystallisation Methods 0.000 abstract description 5
- 230000008025 crystallization Effects 0.000 abstract description 5
- 238000001035 drying Methods 0.000 abstract description 4
- 238000005265 energy consumption Methods 0.000 abstract description 4
- 238000013033 photocatalytic degradation reaction Methods 0.000 abstract description 3
- 229910044991 metal oxide Inorganic materials 0.000 abstract 3
- 229940061607 dibasic sodium phosphate Drugs 0.000 abstract 1
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 abstract 1
- 230000001105 regulatory effect Effects 0.000 abstract 1
- 239000012064 sodium phosphate buffer Substances 0.000 abstract 1
- 239000000243 solution 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
- 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
- 238000003756 stirring Methods 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
- 239000000203 mixture Substances 0.000 description 9
- 239000000839 emulsion Substances 0.000 description 8
- 239000007864 aqueous solution Substances 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 239000013078 crystal Substances 0.000 description 5
- 229910052746 lanthanum Inorganic materials 0.000 description 4
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical group [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 4
- 239000000463 material Substances 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
- 230000000505 pernicious effect Effects 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
- 238000002156 mixing Methods 0.000 description 2
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-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
- 230000000593 degrading effect Effects 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
- 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)
- Cosmetics (AREA)
Abstract
The invention relates to rare earth metal doped nano titanium dioxide, wherein the weight percentage of rare earth metallic oxide on the basis of titanium dioxide is 0.1 to 12 weight percent; and the rare earth metallic oxide is formed by cerium oxide and neodymium oxide, of which the weight ratio is (0.1:1) to (5:1). The invention further relates to a preparation method of the rare earth metal doped nano titanium dioxide, which comprises the following steps: a, adding the rare earth metallic oxide and titanium tetrachloride, which meet the weight percentage and the weight ratio, into water; b, adding citric acid/dibasic sodium phosphate buffer solution; c, regulating a pH value to the range of 5 to 6 by alkali; d, performing reaction at the temperature of 100 to 200 DEG C under the pressure of 0.2 to 0.8MPa; and e, filtering and drying. The invention further relates to application of the rare earth metal doped nano titanium dioxide as a catalyst in a coating. The nano titanium dioxide particles are of an anatase type and have a good crystallization degree; an absorption band of the rare earth metal doped nano titanium dioxide obviously generates red shift in the visible light direction; harmful gas in the environment can be effectively subjected to photocatalytic degradation; and the preparation method of the rare earth metal doped nano titanium dioxide is simple and convenient and is low in energy consumption.
Description
Technical field
The present invention relates to the nano titanium oxide that thulium mixes, prepare the method for the nano titanium oxide that described thulium mixes, and the nano titanium oxide that mixes of described thulium 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 be built comfortable, graceful, elegant living environment, and beautifies people's life.But people are when enjoying everything fine, and house decoration is also constantly strengthening the adverse effect that human body brings pollution and these polluters that living environment causes.At present, the quality of room air has caused the common concern of various circles of society.
Investigation shows that organic pollution materials is nearly more than 500 kinds in the room of fitting up recently, comprise aldehydes, benzene class, ethers, ester class, alcohols, ketone, terpenes etc., wherein there be more than 20 kind of material to have stronger carcinogenic, teratogenesis and mutagenesis, especially formaldehyde, benzene, toluene, ethylbenzene, dimethylbenzene etc. bigger to the harm of human body to human body.
Titanium dioxide has received the increasingly extensive concern of people as photochemical catalyst.Titanium dioxide is as a kind of semiconductor functional material, and its photocatalytic activity is mainly determined by the crystal structure of self.Yet, can improve bands of a spectrum response range and the catalytic efficiency of titanium dioxide by doping vario-property.
Chinese invention patent application CN 1631521 A disclose by co-precipitation-calcination method and have prepared titanium dioxide optical catalyst, wherein in the coprecipitation reaction process, in the weight ratio adding titanium tetrachloride aqueous solution of nitrate with thulium: titanium dioxide=0.5-1.5% with thulium, wherein thulium is selected from lanthanum, cerium, praseodymium, neodymium.
Chinese invention patent application CN 1654335 A disclose the preparation method of visible light photoactivated anatase type TiO 2 sol, and wherein titania-doped salt or its mixture by use lanthanum, cerium, neodymium, europium realized.
Chinese invention patent application CN 102059110 A disclose 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 two kinds of different thuliums are doped in the titanium dioxide simultaneously, under and the situation that the two proportioning is suitable suitable at selected two kinds of thuliums, they will improve the photocatalytic activity of titanium dioxide jointly.
Summary of the invention
In view of above-mentioned prior art situation, the present inventor has carried out research extensively and profoundly in the nano titanium oxide field, in the hope of obtaining the nano titanium oxide that a kind of photocatalytic activity significantly improves.Found that by being 0.1 with weight ratio: 1-5: 1 cerium oxide and neodymia are doped to the nano titanium oxide that can obtain to satisfy above-mentioned requirements in the titanium dioxide.The inventor just is being based on above-mentioned discovery and is finishing the present invention.
The purpose of this invention is to provide a kind of nano titanium oxide, it is doped with cerium oxide and the neodymia of 0.1-12 weight %, and the weight ratio of cerium oxide and neodymia is 0.1: 1-5: 1.
Another object of the present invention provides a kind of method for preparing above-mentioned nano titanium oxide.
A further object of the present invention provides the purposes of above-mentioned nano titanium oxide.
The nano titanium oxide that one aspect of the present invention provides a kind of thulium to mix, wherein rare-earth oxide is 0.1-12 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 for 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 the titanium tetrachloride that will satisfy described percetage by weight and weight ratio is added to the water;
B) add citric acid/dibastic sodium phosphate cushioning liquid;
C) with alkali the pH value is adjusted to 5-6;
D) under the pressure of 100-200 ℃ temperature and 0.2-0.8MPa, react; With
E) filtration and dry.
Further aspect of the present invention provides nano titanium oxide that above-mentioned thulium the mixes purposes as photochemical catalyst in coating.
The nano titanium oxide that thulium of the present invention mixes is Detitanium-ore-type, and crystallization degree is good; Its absorption band is to the obvious red shift of visible light direction; Pernicious gas in the photocatalytic degradation environment effectively; Its preparation method is simple and convenient and energy consumption is low.
These and other purposes, features and advantages of the present invention will be easy to be understood by those of ordinary skill after considering the present invention in conjunction with following accompanying drawing integral body.
Description of drawings
Fig. 1 is the transmission electron microscope photo of the colloidal dispersion of the embodiment of the invention 1.
Fig. 2 is the X-ray diffractogram of the nano titanium oxide that mixes of the thulium of the embodiment of the invention 1.
Fig. 3 shows the absorbance of nano titanium oxide in the 200-1200nm wave-length coverage of the thulium doping of the embodiment of the invention 1.
The specific embodiment
The nano titanium oxide that thulium of the present invention mixes is made up of titanium dioxide and the rare-earth oxide that is entrained in wherein.
Absorption band red shift gradually along with the increase of thulium doping of the nano titanium oxide that thulium mixes, its absorptivity to visible light obviously increases.Yet along with the increase of thulium doping, the anatase peak-to-peak signal of nano titanium oxide in XRD that thulium mixes weakens gradually, and the doping of this explanation thulium has suppressed the growth of anatase crystal to a certain extent.
Therefore, in the nano titanium oxide that thulium of the present invention mixes, rare-earth oxide is 0.1-12 weight % based on the percetage by weight of titanium dioxide, preferred 1-8 weight %, more preferably 2-5 weight %.
Be lower than under the situation of 0.1 weight % in the percetage by weight of rare-earth oxide based on titanium dioxide, absorption band is not obvious to the red shift of visible light; Be higher than under the situation of 12 weight % in the percetage by weight of rare-earth oxide based on titanium dioxide, the growth of anatase crystal has been subjected to largely suppressing, its respective peaks signal in XRD a little less than, and cost obviously increases.
In the nano titanium oxide that thulium of the present invention mixes, 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, preferred 0.3: 1-3: 1, more preferably 0.5: 1-2: 1.
The weight ratio of cerium oxide and neodymia less than 0.1: 1 situation under, the hole of generation is not enough, and then causes absorption band not obvious to the red shift of visible light; The weight ratio of cerium oxide and neodymia greater than 5: 1 situation under, nano titanium dioxide crystal form will be a greater impact to the transformation of Detitanium-ore-type.
The feature of the nano titanium oxide that thulium of the present invention mixes is that also it is the form of solid solution, and wherein thulium has entered in the titanium dioxide crystal lattice.
The particle diameter of the nano titanium oxide that thulium of the present invention mixes is 10-80nm, preferred 20-50nm.
The nano titanium oxide that thulium of the present invention mixes is Detitanium-ore-type, and crystallization degree is good.
Compare with the nano titanium oxide that does not have to mix, the absorption band of the nano titanium oxide that thulium of the present invention mixes is to the red shift of visible light direction, and its absorptivity to visible light obviously increases.
The nano titanium oxide that thulium of the present invention mixes can prepare by the following method:
A) rare-earth oxide and the titanium tetrachloride that will satisfy above-mentioned percetage by weight and weight ratio is added to the water;
B) add citric acid/dibastic sodium phosphate cushioning liquid;
C) with alkali the pH value is adjusted to 5-6; With
D) under the pressure of 100-200 ℃ temperature and 0.2-0.8MPa, react; With
E) filtration and dry.
Step a)
Particularly, step a) is performed as follows usually: the rare-earth oxide that at first will satisfy above-mentioned percetage by weight adds in the titanium tetrachloride, and the mixture with gained rare-earth oxide and titanium tetrachloride is added to the water at last.
Above-mentioned percetage by weight refers to that specifically rare-earth oxide is 0.1-12 weight % based on the titanium dioxide in the nano titanium oxide of thulium doping of the present invention, preferred 1-8 weight %, more preferably 2-5 weight %.
Used rare-earth oxide is preferably the mixture of cerium oxide and neodymia.
For this reason, before adding rare-earth oxide in the titanium tetrachloride, the cerium oxide and the neodymia that need to satisfy above-mentioned weight ratio mix.
Above-mentioned weight ratio refers to that specifically the weight ratio of cerium oxide and neodymia is 0.1: 1-5: 1, preferred 0.3: 1-3: 1, more preferably 0.5: 1-2: 1.
Rare-earth oxide carried out in closed reaction vessel with mixing usually of titanium tetrachloride.If desired, described mixing also can be carried out in inert gas such as nitrogen atmosphere.
Usually at room temperature the mixture of gained rare-earth oxide and titanium tetrachloride is added to the water stirring simultaneously.Suitable is that the weight ratio of titanium tetrachloride and water is 1: 8-1: 15.Thereby control adds the speed of the mixture of rare-earth oxide and titanium tetrachloride makes the hydrolysis of titanium tetrachloride and water leniently carry out with controlled manner.After adding, continue to stir so that titanium tetrachloride continues hydrolysis 30-90 minute.
As optional embodiment, also can successively rare-earth oxide and the titanium tetrachloride that satisfies above-mentioned percetage by weight and weight ratio be added to the water.
As optional embodiment, also can simultaneously rare-earth oxide and the titanium tetrachloride that satisfies above-mentioned percetage by weight and weight ratio be added to the water.
In described two kinds of optional embodiments, concrete operations just wherein mix rare-earth oxide earlier as mentioned with titanium tetrachloride, and the embodiment that the gained mixture is added to the water is described then.Perhaps, can carry out appropriate change to described concrete operations according to actual needs.
Step b)
In step b), citric acid/dibastic sodium phosphate cushioning liquid (aqueous solution) is added in the step a) gained mixed system.The pH value of citric acid/dibastic sodium phosphate cushioning liquid is 5-6 suitably, for example 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, utilize alkali that the pH value of step b) gained mixed system is adjusted to 5-6.Used alkali can be alkali metal hydroxide, alkaline earth metal hydroxide or ammonia, preferred alkali metal hydroxide, especially NaOH.Alkali can the solid pure material form use, for example use solid sodium hydroxide.At this moment, add the alkali of described solid form usually in batches, for example stir the alkali that adds 4/9,3/9 and 2/9 aequum down successively.Alkali also can the aqueous solution form use, for example use sodium hydrate aqueous solution.At this moment, add the alkali of described aqueous solution form usually with the concentration gradient of successively decreasing in batches, for example stir the alkali that adds 6M, 4M and 2M down successively.Those skilled in the art can determine the consumption of alkali easily according to required target pH value.
Step d)
In this step, make the reaction under the pressure of 100-200 ℃ temperature and 0.2-0.8MPa of step c) gained mixed system form colloidal dispersion.
Reaction temperature is preferably 150-180 ℃.Reaction pressure is preferably 0.4-0.6MPa.Be lower than 100 ℃ or reaction pressure in reaction temperature and be lower than under the situation of 0.2MPa, the amount of the nano titanium oxide that the Detitanium-ore-type thulium mixes is not enough; Simultaneously, should avoid reaction temperature to be higher than 200 ℃ or reaction pressure usually and be higher than 0.8MPa because this moment reaction system energy consumption and danger all unnecessarily increase.
Carry out in the described closed container that is reflected at high temperature resistant and high pressure, for example in reactor, carry out.
Reaction time is selected so that the hydroxide in the step c) gained mixed system is converted into corresponding oxide as much as possible.In the gained colloidal dispersion, the nano titanium oxide that mixes as the thulium of solids is for more than at least 80 weight %, preferably more than at least 85 weight %, more preferably more than at least 90 weight %, for example 91 weight % or 92 weight %, described percetage by weight is in each case all based on the gross weight of the solids that are present in continuous aqueous phase.Generally speaking, the reaction time is generally 1-3 hour.
Step e)
In this step, step d) gained colloidal dispersion is filtered and the dry nano titanium oxide that obtains thulium doping of the present invention.
After filtering as suction filtration and before the drying, can choose wantonly and wash to remove hydrochloride attached thereto as much as possible to filtering the gained solid, but this is optional.Drying is for example carried out under 55-75 ℃ the temperature usually below 100 ℃.
The nano titanium oxide that thulium of the present invention mixes is suitable for photocatalyst because of the obvious red shift of its absorption band, pernicious gas such as formaldehyde and toluene in the environment of degrading effectively.
For this reason, the nano titanium oxide that thulium of the present invention can be mixed directly or after disperseing adds in the existing coating again, for example adds in the commercial coating.Perhaps, also colloidal dispersion according to the present invention directly can be added in the existing coating.The nm TiO 2-base that thulium mixes is 30-50 weight % in the gross weight of existing coating.
Nano titanium oxide that thulium of the present invention mixes 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 of visible light direction;
4. pernicious gas such as toluene and the formaldehyde in the photocatalytic degradation environment more effectively; With
5. by preparing comprising the method for reacting under the pressure of 100-200 ℃ temperature and 0.2-0.8MPa, described method is simple and convenient, has avoided high energy consumption and therefore expensive calcining step.
Embodiment
Hereinafter by reference example and accompanying drawing the present invention is specifically described, but described embodiment does not constitute any restriction to the scope of the invention.
Transmission electron microscope: company of NEC, JEM-2100 type; Ultraviolet spectrophotometer: HITACHI, the U-3010 type; X-ray diffractometer: day island proper Tianjin, 7000S type.
Embodiment 1
500 gram rare-earth oxides (weight ratio of cerium oxide and neodymia is 0.8: 1) are added in the 40kg titanium tetrachloride, stirred 1 hour; It is added in the 400kg water, stirred 40 minutes; Be citric acid/dibastic sodium phosphate cushioning liquid 40kg of 5.5 to wherein adding the pH value; PH value to 5.2 with the sodium hydrate solid regulation system; 20kg gained mixed system is added in the reactor, and reaction 60 minutes under the condition of 155 ℃ and 0.44MPa; With a part react gained colloidal dispersion (15kg) add 25kg benzene emulsion (the Nantong life reaches chemical industry Co., Ltd, S-01) in, stir.
Fig. 1 shows the transmission electron microscope picture of described colloidal dispersion, and its particle diameter that shows wherein the nano titanium oxide that the thulium that exists as solids mixes is 20-50nm.
With the described colloidal dispersion suction filtration of part, washing 65 ℃ of dryings 10 hours, is ground and is obtained the nano titanium oxide fine particle that thulium mixes, and its X-ray diffractogram and the absorbance in the 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 that its absorption band is obviously to the red shift of visible light direction.
1000 gram rare-earth oxides (weight ratio of cerium oxide and neodymia is 1: 1) are added in the 40kg titanium tetrachloride, stirred 1 hour; It is added in the 400kg water, stirred 45 minutes; Be citric acid/dibastic sodium phosphate cushioning liquid 40kg of 5.5 to wherein adding the pH value; PH value to 5.4 with the sodium hydrate solid regulation system; 20kg gained mixed system is added in the reactor, and reaction 65 minutes under the condition of 160 ℃ and 0.48MPa; Reaction gained colloidal dispersion is added in the benzene emulsion of 35kg, stir.
Embodiment 3
1500 gram rare-earth oxides (weight ratio of cerium oxide and neodymia is 1.2: 1) are added in the 40kg titanium tetrachloride, stirred 1 hour; It is added in the 320kg water, stirred 50 minutes; Be citric acid/dibastic sodium phosphate cushioning liquid 40kg of 5.5 to wherein adding the pH value; PH value to 5.6 with the sodium hydrate solid regulation system; 20kg gained mixed system is added in the reactor, and reaction 70 minutes under the condition of 175 ℃ and 0.52MPa; Reaction gained colloidal dispersion is added in the benzene emulsion of 40kg, stir.
Embodiment 4
2000 gram rare-earth oxides (weight ratio of cerium oxide and neodymia is 1.4: 1) are added in the 40kg titanium tetrachloride, stirred 1 hour; It is added in the 600kg water, stirred 55 minutes; Be citric acid/dibastic sodium phosphate cushioning liquid 40kg of 5.5 to wherein adding the pH value; PH value to 5.8 with the sodium hydrate solid regulation system; 20kg gained mixed system is added in the reactor, and reaction 75 minutes under the condition of 170 ℃ and 0.56MPa; Reaction gained colloidal dispersion is added in the benzene emulsion of 45kg, stir.
The comparative example 1
The 40kg titanium tetrachloride is added in the 400kg water, stirred 40 minutes; Be citric acid/dibastic sodium phosphate cushioning liquid 40kg of 5.5 to wherein adding the pH value; PH value to 5.2 with the sodium hydrate solid regulation system; 20kg gained mixed system is added in the reactor, and reaction 60 minutes under the condition of 165 ℃ and 0.44MPa; Reaction gained colloidal dispersion is added in the benzene emulsion of 25kg, stir.
The comparative example 2
1000 gram lanthanas are added in the 40kg titanium tetrachloride, stirred 1 hour; It is added in the 400kg water, stirred 45 minutes; Be citric acid/dibastic sodium phosphate cushioning liquid 40kg of 5.5 to wherein adding the pH value; PH value to 5.2 with the sodium hydrate solid regulation system; 20kg gained mixed system is added in the reactor, and reaction 60 minutes under the condition of 165 ℃ and 0.46MPa; Reaction gained colloidal dispersion is added in the benzene emulsion of 25kg, stir.
The comparative example 3
1500 gram yittrium oxide are added in the 40kg titanium tetrachloride, stirred 1 hour; It is added in the 400kg water, stirred 50 minutes; Be citric acid/dibastic sodium phosphate cushioning liquid 40kg of 5.5 to wherein adding the pH value; PH value to 5.2 with the sodium hydrate solid regulation system; 20kg gained mixed system is added in the reactor, and reaction 60 minutes under the condition of 170 ℃ and 0.52MPa; Reaction gained colloidal dispersion is added in the benzene emulsion of 25kg, stir.
The comparative example 4
2000 gram europium oxides are added in the 40kg titanium tetrachloride, stirred 1 hour; It is added in the 400kg water, stirred 55 minutes; Be citric acid/dibastic sodium phosphate cushioning liquid 40kg of 5.5 to wherein adding the pH value; PH value to 5.2 with the sodium hydrate solid regulation system; 20kg gained mixed system is added in the reactor, and reaction 60 minutes under the condition of 175 ℃ and 0.58MPa; Reaction gained colloidal dispersion is added in the benzene emulsion of 25kg, stir.
Performance test
Embodiment 1-4 and the described final products of 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.The gained result is as shown in the table.
Claims (10)
1. the nano titanium oxide that mixes of a thulium, wherein rare-earth oxide is 0.1-12 weight % based on the percetage by weight of titanium dioxide, preferred 1-8 weight %, more preferably 2-5 weight %, rare-earth oxide is cerium oxide and neodymia, the weight ratio of cerium oxide and neodymia is 0.1: 1-5: 1, preferred 0.3: 1-3: 1, more preferably 0.5: 1-2: 1.
2. the nano titanium oxide that mixes of thulium as claimed in claim 1, the particle diameter of the nano titanium oxide that described thulium mixes is 10-80nm.
3. the nano titanium oxide that mixes of thulium as claimed in claim 2, the particle diameter of the nano titanium oxide that described thulium mixes is 20-50nm.
4. as the nano titanium oxide of each described thulium doping among the claim 1-3, it prepares by following steps:
A) rare-earth oxide and the titanium tetrachloride that will satisfy described percetage by weight and weight ratio is added to the water;
B) add citric acid/dibastic sodium phosphate cushioning liquid;
C) with alkali the pH value is adjusted to 5-6;
D) at 100-200 ℃, preferred 150-180 ℃ temperature and 0.2-0.8MPa react under the pressure of preferred 0.4-0.6MPa; With
E) filtration and dry.
5. the nano titanium oxide that mixes of thulium as claimed in claim 4, wherein the weight ratio of titanium tetrachloride and water is 1: 8-1: 15.
6. the nano titanium oxide that mixes of thulium as claimed in claim 4, wherein used alkali is alkali metal hydroxide, alkaline earth metal hydroxide or ammonia.
7. method for preparing among the claim 1-3 nano titanium oxide that each described thulium mixes said method comprising the steps of:
A) rare-earth oxide and the titanium tetrachloride that will satisfy described percetage by weight and weight ratio is added to the water;
B) add citric acid/dibastic sodium phosphate cushioning liquid;
C) with alkali the pH value is adjusted to 5-6;
D) at 100-200 ℃, preferred 150-180 ℃ temperature and 0.2-0.8MPa react under the pressure of preferred 0.4-0.6MPa; With
E) filtration and dry.
8. method as claimed in claim 7, wherein the weight ratio of titanium tetrachloride and water is 1: 8-1: 15.
9. method as claimed in claim 7, wherein used alkali is alkali metal hydroxide, alkaline earth metal hydroxide or ammonia.
The nano titanium oxide that mixes as each described thulium among the claim 1-6 in coating as the purposes of photochemical catalyst.
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| CN105080531A (en) * | 2015-08-13 | 2015-11-25 | 上海工程技术大学 | Method for preparing neodymium-doped mesopore titanium dioxide microballoon photocatalyst |
| 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 |
| CN113318726A (en) * | 2020-02-28 | 2021-08-31 | 广东粤能净环保科技有限公司 | Photocatalyst with negative oxygen ion releasing function and preparation method and application thereof |
| CN113318721A (en) * | 2020-02-28 | 2021-08-31 | 广东粤能净环保科技有限公司 | Photocatalytic unit with negative oxygen ion releasing function and application thereof |
| CN113318726B (en) * | 2020-02-28 | 2023-08-01 | 中科粤能净(山东)新材料有限公司 | Photocatalyst with function of releasing negative oxygen ions and preparation method and application thereof |
| CN113318721B (en) * | 2020-02-28 | 2023-08-01 | 中科粤能净(山东)新材料有限公司 | Photocatalysis unit with negative oxygen ion release function and application thereof |
| CN114751449A (en) * | 2021-01-08 | 2022-07-15 | 北京化工大学 | Preparation method and application of metal-doped nano titanium dioxide aqueous phase dispersion |
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