CN105603526A - Nano-TiO2 single-crystal material, preparation method thereof and application thereof - Google Patents
Nano-TiO2 single-crystal material, preparation method thereof and application thereof Download PDFInfo
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- 239000000463 material Substances 0.000 title claims abstract description 46
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 43
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 239000013078 crystal Substances 0.000 title abstract description 12
- 238000000034 method Methods 0.000 claims abstract description 28
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 19
- 238000006243 chemical reaction Methods 0.000 claims abstract description 18
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 claims abstract description 13
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 claims abstract description 13
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 claims abstract description 13
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000005642 Oleic acid Substances 0.000 claims abstract description 13
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 claims abstract description 13
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 claims abstract description 13
- 239000000203 mixture Substances 0.000 claims abstract description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 84
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 30
- 239000000243 solution Substances 0.000 claims description 25
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 21
- 239000008367 deionised water Substances 0.000 claims description 18
- 229910021641 deionized water Inorganic materials 0.000 claims description 18
- 238000005406 washing Methods 0.000 claims description 18
- 239000011259 mixed solution Substances 0.000 claims description 15
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 15
- 239000013049 sediment Substances 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 12
- 238000001556 precipitation Methods 0.000 claims description 9
- 238000010992 reflux Methods 0.000 claims description 9
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 claims description 8
- 239000003054 catalyst Substances 0.000 claims description 7
- 238000007710 freezing Methods 0.000 claims description 4
- 230000008014 freezing Effects 0.000 claims description 4
- 238000004108 freeze drying Methods 0.000 claims description 3
- 125000003277 amino group Chemical group 0.000 claims 2
- 239000002245 particle Substances 0.000 abstract description 31
- QGLWBTPVKHMVHM-KTKRTIGZSA-N (z)-octadec-9-en-1-amine Chemical compound CCCCCCCC\C=C/CCCCCCCCN QGLWBTPVKHMVHM-KTKRTIGZSA-N 0.000 abstract description 12
- 230000001699 photocatalysis Effects 0.000 abstract description 6
- 239000000654 additive Substances 0.000 abstract description 5
- 230000000996 additive effect Effects 0.000 abstract description 4
- 238000005265 energy consumption Methods 0.000 abstract description 2
- 239000002086 nanomaterial Substances 0.000 abstract description 2
- 238000002425 crystallisation Methods 0.000 abstract 1
- 230000008025 crystallization Effects 0.000 abstract 1
- 239000002355 dual-layer Substances 0.000 abstract 1
- 235000019441 ethanol Nutrition 0.000 description 23
- 238000009826 distribution Methods 0.000 description 6
- 239000002244 precipitate Substances 0.000 description 6
- 239000000839 emulsion Substances 0.000 description 5
- RBTBFTRPCNLSDE-UHFFFAOYSA-N 3,7-bis(dimethylamino)phenothiazin-5-ium Chemical compound C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 RBTBFTRPCNLSDE-UHFFFAOYSA-N 0.000 description 4
- 238000005119 centrifugation Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 4
- 229960000907 methylthioninium chloride Drugs 0.000 description 4
- 150000001412 amines Chemical group 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 238000005755 formation reaction Methods 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- HXQHFNIKBKZGRP-URPRIDOGSA-N (5Z,9Z,12Z)-octadecatrienoic acid Chemical compound CCCCC\C=C/C\C=C/CC\C=C/CCCC(O)=O HXQHFNIKBKZGRP-URPRIDOGSA-N 0.000 description 2
- HXQHFNIKBKZGRP-UHFFFAOYSA-N Ranuncelin-saeure-methylester Natural products CCCCCC=CCC=CCCC=CCCCC(O)=O HXQHFNIKBKZGRP-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 239000000975 dye Substances 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 238000007146 photocatalysis Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 235000021081 unsaturated fats Nutrition 0.000 description 2
- 206010037660 Pyrexia Diseases 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003933 environmental pollution control Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 230000002045 lasting effect Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 1
- 238000000593 microemulsion method Methods 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- -1 papermaking Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- DCKVNWZUADLDEH-UHFFFAOYSA-N sec-butyl acetate Chemical compound CCC(C)OC(C)=O DCKVNWZUADLDEH-UHFFFAOYSA-N 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 238000002336 sorption--desorption measurement Methods 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
- C30B29/10—Inorganic compounds or compositions
- C30B29/16—Oxides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/063—Titanium; Oxides or hydroxides thereof
-
- B01J35/39—
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
- C30B29/60—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape characterised by shape
-
- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B7/00—Single-crystal growth from solutions using solvents which are liquid at normal temperature, e.g. aqueous solutions
- C30B7/10—Single-crystal growth from solutions using solvents which are liquid at normal temperature, e.g. aqueous solutions by application of pressure, e.g. hydrothermal processes
Abstract
The invention belongs to the field of inorganic nanomaterial preparation and particularly relates to a nano-TiO2 single-crystal material, a preparation method thereof and an application thereof. The method comprises the steps of performing a hydrothermal reaction by adopting a dual-layer reaction kettle liner; taking oleic acid and oleylamine as additives, and controlling the additive amounts of oleic acid and oleylamine; and adjusting the composition and additive amount of a water-alcohol solution, so that anatase type nano-TiO2 single-crystal particles uniform in size and high in crystallization degree are prepared, wherein the anatase type nano-TiO2 single-crystal particles have the mean particle size of 7nm and the relative standard deviation of less than 9%. The nano-TiO2 prepared with the method is regular in morphology, high in product purity and good in dispersity, and has relatively high photocatalytic activity; and the preparation method for the nano-TiO2 single-crystal material is simple to operate, environment-friendly, mild in reaction condition, low in energy consumption and easy to popularize and use.
Description
Technical field
The invention belongs to technical field of nano material, relate to a kind of nano-TiO2Monocrystal material, preparation method andIts purposes, relates in particular to a kind of nano-TiO with height homogeneous granularity2Monocrystal material, preparation method, withAnd in the purposes of photocatalysis field.
Background technology
TiO2Have that photocatalytic activity is high, environmental friendliness and the advantage such as with low cost, be efficiency light of greatest concernCatalyst, was widely used in environmental pollution control, coating, papermaking, rubber, closes from the middle of last centuryBecome the fields such as fiber, pottery, electronics and metallurgy. TiO2The performance of material depend primarily on its crystal formation, crystal face,Pattern and particle diameter. Therefore, control the synthetic TiO with different shape and particle diameter2Structure becomes current researchFocus. TiO2There are brockite, anatase and three kinds of common crystal formations of rutile, wherein anatase TiO2At lightThe aspect such as catalysis and solar cell shows excellent performance. The TiO that size is little2There is larger specific surfaceLong-pending, high-specific surface area contributes to improve absorption and the refractive index of light, is conducive to reactant in surperficial absorption,Make TiO2There is higher photocatalytic activity; For ensureing TiO2Stable performance in lasting research and application,Synthetic TiO2Material should have crystal structure, and particle scale should keep homogeneous; Meanwhile, size distribution is equalOne nano-TiO2There is very important application in metering and field fo standardization. Therefore, prepared sizes homogeneousAnatase crystal nano-TiO2Material has great importance.
At present, nano-TiO2The preparation method of material mainly contains chemical hydro-thermal method, Hydrolyze method, the hot method of alcohol, heavyShallow lake method, sol-gel process and microemulsion method etc., wherein, hydro-thermal method is a kind of common method. Hydro-thermal method beIn autoclave reactor, adopt the aqueous solution as reaction medium, heat by reaction vessel, create one highTemperature reaction under high pressure environment, makes presoma reaction. Hydro-thermal method can directly make well-crystallized's powder, does not need to doHigh-temperature process, has avoided the powder hard aggregation that may form in this process, and by changing process conditions,Can realize the control to the characteristic such as diameter of particle, crystal formation, meanwhile, the powder purity making is high.
CN103964502A discloses a kind of nano-TiO2Monocrystal material and its production and use, its profitCombine with hydrothermal synthesis method with collosol and gel, first obtain gel in stirring at room temperature, then will obtain gel centrifugalWhite precipitate be distributed to 120～150 DEG C of hydro-thermals in water alcohol system, obtain the nano-TiO of particle diameter at 10～15nm2Material, but the nano-TiO obtaining by the method2Size all more than 10nm, and can not get less chiVery little nano-TiO2Material.
Therefore, be necessary to study one and prepare nano-TiO2The method of material, to prepare the more nanometer of small particle diameterTiO2Material.
Summary of the invention
The object of this invention is to provide a kind of particle diameter is 7nm, relative standard deviation below 9%, size distributionThe anatase type nano TiO of homogeneous2Monocrystal material, preparation method and its usage.
First aspect, the invention provides a kind of nano-TiO2Monocrystal material, described nano-TiO2Material is sharp titaniumOre deposit type TiO2, size distribution homogeneous, average grain diameter is 7nm, relative standard deviation, below 9%, is marked relativelyAccurate deviation for example can be 9%, 8%, 7.5%, 7%, 6%, 5%, 4%, 3%, 2%, 1% or 0 etc.,Known by this statement, nano-TiO of the present invention2Particle diameter at 7 × (1-9%)=6.37nm to 7 × (1+9%)Between=7.63nm, any other statement but actual particle size drop on 6.37nm between 7.63nm, also belong toProtection scope of the present invention. Illustrate: particle diameter is 7.2nm, relative standard deviation is 5%, its representativeParticle size range is actually 6.48nm to 7.56nm, has dropped on 6.37nm of the present invention to 7.63nm'sWithin scope, thereby also belong to protection scope of the present invention.
Second aspect, the invention provides a kind of nano-TiO of preparing described in first aspect2The method of monocrystal material,Comprise the following steps:
(1) deionized water of 1～7 parts by volume is mixed with the ethanol of 19～13 parts by volume, stir evenly, obtain waterAlcoholic solution, proceeds in inner bag, and water-alcohol solution accounts for 14～26% of reactor inner bag volume;
(2) butyl titanate of 1.8 parts by volume is joined by the oleic acid of 9.5 parts by volume, the oil of 6.5 parts by volumeIn the mixed system of the ethanol composition of amine and 6.0 parts by volume, obtain mixed solution, proceed in inner bag;
(3) the described inner bag of step (2) is inserted in the described inner bag of step (1), wherein, step (2)The ratio of the volume of the described inner bag of the volume of described inner bag and step (1) is 2:5, carries out hydro-thermal reaction, obtainsNano-TiO2Monocrystal material.
The present invention is using oleic acid and oleyl amine as additive, and controls the addition of oleic acid and oleyl amine, regulation and control nanometerTiO2The pattern of material and size, unsaturated fat pinolenic acid and unsaturated amine oleyl amine can in hydro-thermal reactionReduce the hydrolysis rate of butyl titanate, and then affect nano-TiO2Particle diameter, meanwhile, the present invention adopts bilayerReactor inner bag carries out hydro-thermal reaction, and the water-alcohol solution in outer field reactor inner bag is in hydrothermal reaction processManufacture the reaction environment of water alcohol steam, regulate composition and the addition of water-alcohol solution, can regulate and control equally metatitanic acidThe hydrolysis rate of butyl ester and the nano-TiO of generation2Particle diameter.
Ethanol of the present invention is absolute ethyl alcohol.
Preferably, in the described water-alcohol solution of step (1), the consumption of deionized water is 1～7 parts by volume, for exampleCan be 1 parts by volume, 2 parts by volume, 3 parts by volume, 4 parts by volume, 5.5 parts by volume, 6 parts by volume or 7 volumesPart etc., be preferably 2～5 parts by volume.
Preferably, in the described water-alcohol solution of step (1), the consumption of ethanol is 19～13 parts by volume, for example canBe 19 parts by volume, 18 parts by volume, 17 parts by volume, 16 parts by volume, 15 parts by volume, 14 parts by volume or 13Parts by volume etc., are preferably 18～15 parts by volume.
Preferably, water-alcohol solution accounts for 14～26% of reactor inner bag 1 volume, for example can be 14%, 15%,16%, 17%, 18%, 18.5%, 19%, 20%, 21%, 22%, 23%, 24%, 25% or 26%Deng.
Preferably, in the described water-alcohol solution of step (1), the volume ratio of deionized water and ethanol is (2～5):(18～15), for example, can be 2:18,3:17,4:16 or 5:15 etc.
Inner bag of the present invention is reactor inner bag, is preferably polytetrafluoroethylliner liner.
In the present invention, the ratio of the volume of the volume of the described inner bag of step (2) and the described inner bag of step (1) is2:5, illustrates, and the volume of the described inner bag of step (2) is 40mL, and the body of the described inner bag of step (1)Amass as 100mL. Or the volume of the described inner bag of step (2) is 200mL, and the described inner bag of step (1)Volume be 500mL. The volume of the described inner bag of step in the present invention (2) and the described inner bag of step (1) withoutConcrete restriction, as long as can meet the volume of the described inner bag of step (2) and the volume of the described inner bag of step (1)Ratio be 2:5, those skilled in the art can select as required, and determining step (1) ordinatedlyThe consumption of each component in the consumption of middle water-alcohol solution and step (2), " ordinatedly " refers to step (1) instituteState inner bag volume determine after, the consumption of water-alcohol solution accounts for the described inner bag volume of step (1) according to water-alcohol solution14～26% standard use, contrary, the Determination of quantity of water-alcohol solution later also will be according to same markStandard is selected the volume of the described inner bag of step (1).
Preferably, the time of the described hydro-thermal reaction of step (3) is 6～18h, for example can be 6h, 7h, 8h,8.5h, 9h, 10h, 11h, 11.5h, 12h, 13h, 14h, 14.5h, 15h, 16h, 17h or 18h etc.
Preferably, the temperature of hydro-thermal reaction is 180～200 DEG C, for example can be 180 DEG C, 185 DEG C, 188 DEG C,190 DEG C, 195 DEG C or 200 DEG C etc.
Preferably, described method is also included in after reaction finishes carries out step (4) and step (5) successively, itsIn, step (4) is: the white emulsion that step (3) hydro-thermal reaction is obtained is centrifugal, obtains centrifugalPrecipitation be dispersed in cyclohexane and reflux; Step (5) is: the sediment that washing step (4) obtains, andFreeze drying.
Preferably, the centrifugal precipitation obtaining is dispersed in the cyclohexane of 50 parts by volume and refluxes, the temperature of backflowBe preferably 60～80 DEG C, for example, can be 60 DEG C, 65 DEG C, 70 DEG C, 74 DEG C, 78 DEG C or 80 DEG C etc., backflowTime is preferably 2～6h, and the time of backflow for example can be 2h, 3h, 4h, 5h or 6h etc.
It is to remove unreacted oleic acid that the centrifugal precipitation obtaining is distributed to the object refluxing in cyclohexane by the present inventionAnd oleyl amine, because unsaturated fat pinolenic acid and unsaturated amine oleyl amine are as the polymer substance of long-chain, logicalCross conventional washing and be difficult to remove totally, therefore the present invention is distributed in cyclohexane by precipitation and refluxes behaviourDo.
Preferably, the washing in step (5) is the mixed solution washing precipitate of first using cyclohexane and ethanol,Use again deionized water washing sediment, by continue afterwards the mixed solution washing with cyclohexane and ethanol in backflowAnd further with deionized water washing, can obtain that purity is high, the nano-TiO of good dispersion2Material.
Preferably, in the mixed solution of described cyclohexane and ethanol, the volume ratio of cyclohexane and ethanol is 1:8.
Preferably, in step (5), cryodesiccated temperature is-75～-50 DEG C, for example can be-75 DEG C ,-70 DEG C,-68 DEG C ,-65 DEG C ,-60 DEG C ,-55 DEG C or-50 DEG C etc.
It should be noted that: in the present invention, parts by volume refers between various reactants proportionate relationship by volume,The measurement unit of parts by volume does not limit, and can be any volume metering unit such as mL or L.
In the third aspect, the invention provides a kind of nano-TiO as described in first aspect2Monocrystal material is as lightThe purposes of catalyst.
Compared with prior art, beneficial effect of the present invention is as follows:
(1) the present invention adopts oleic acid and oleyl amine as additive and regulates its addition, adjusting butyl titanateHydrolysis rate, and then regulation and control nano-TiO2The pattern of material and size, meanwhile, the present invention adopts double-deck reactionStill inner bag carries out hydro-thermal reaction, and the water-alcohol solution in outer field reactor inner bag is manufactured in hydrothermal reaction processThe reaction environment of water alcohol steam, regulates composition and the addition of water-alcohol solution, and then regulates and controls the nano-TiO of generation2Particle diameter. The TiO that adopts method of the present invention to obtain2Granule-morphology rule, better crystallinity degree, size are equalEven, particle diameter is 7nm, relative standard deviation below 9%, good dispersion and product purity high, and haveHigh photocatalytic activity;
(2) simple to operate, the environmental friendliness of preparation method of the present invention, reaction condition gentleness, energy consumption are low,Be easy to promote the use of.
Brief description of the drawings
Fig. 1 is the TiO that the embodiment of the present invention 1 makes2The transmission electron microscope picture of monocrystal material;
Fig. 2 is the TiO that the embodiment of the present invention 1 makes2The XRD figure of monocrystal material;
Fig. 3 is the nano-TiO that the embodiment of the present invention 1 makes2Monocrystal material (B) is received with commercially available commercializationRice TiO2Material (A) degradation of methylene blue photocatalysis effect comparison diagram.
Detailed description of the invention
Further illustrate technical scheme of the present invention below in conjunction with accompanying drawing and by detailed description of the invention.
Embodiment 1
(1) deionized water of 2mL is added drop-wise in 18mL absolute ethyl alcohol, stirs, be placed in 100mLIn polytetrafluoroethylliner liner;
(2) 1.8mL butyl titanate is added to 9.5mL oleic acid, 6.5mL oleyl amine, 6.0mL absolute ethyl alcoholIn mixed system, stir, obtain light yellow transparent solution, be placed in 40mL polytetrafluoroethylliner liner;
(3) 40mL polytetrafluoroethylliner liner is inserted in 100mL polytetrafluoroethylliner liner, is then placed in anti-Answer in still 180 DEG C of reactions 6 hours;
(4) after completion of the reaction,, by the white emulsion centrifugation obtaining, precipitation is dispersed in to 50mL ringIn hexane, reflux 6 hours in 80 DEG C;
(5) the mixed solution washing precipitate of use cyclohexane and ethanol, in the mixed solution of cyclohexane and ethanol,The volume ratio of cyclohexane and ethanol is 1:8, then uses deionized water washing sediment. Sediment is freezing in-75 DEG CBe dried, obtain the Detitanium-ore-type TiO of size distribution homogeneous2Monocrystal material.
The prepared TiO of the present embodiment2Monocrystal material comprises a large amount of pattern rules, size uniform, good dispersionNano particle, the particle diameter of particle is 7.0nm, relative standard deviation is 9%.
Can find out Titanium dioxide nanoparticle granularity prepared by the present invention from the transmission electron microscope picture shown in Fig. 1Be evenly distributed, good dispersion. Through the statistics of 500 above particles, its particle diameter distributes and is about 7.0 ± 0.6nm.
Can find out the respectively corresponding Detitanium-ore-type oxidation in the position at 5 peaks in figure from the XRD figure shown in Fig. 2The different crystal faces of titanium, therefore show that titania meterial prepared by the present invention is Detitanium-ore-type.
Embodiment 2
(1) deionized water of 5mL is added drop-wise in 15mL absolute ethyl alcohol, stirs, be placed in 100mLIn polytetrafluoroethylliner liner;
(2) 1.8mL butyl titanate is added to 9.5mL oleic acid, 6.5mL oleyl amine, 6.0mL absolute ethyl alcoholIn mixed system, stir, obtain light yellow transparent solution, be placed in 40mL polytetrafluoroethylliner liner;
(3) 40mL polytetrafluoroethylliner liner is inserted in 100mL polytetrafluoroethylliner liner, is then placed in anti-Answer in still 200 DEG C of reactions 18 hours;
(4) after completion of the reaction,, by the white emulsion centrifugation obtaining, precipitation is dispersed in to 50mL ringIn hexane, reflux 2 hours in 80 DEG C;
(5) the mixed solution washing precipitate of use cyclohexane and ethanol, in the mixed solution of cyclohexane and ethanol,The volume ratio of cyclohexane and ethanol is 1:8, then uses deionized water washing sediment. Sediment is freezing in-50 DEG CBe dried, obtain the Detitanium-ore-type TiO of size distribution homogeneous2Monocrystal material.
The prepared TiO of the present embodiment2Monocrystal material comprises a large amount of pattern rules, size uniform, good dispersionNano particle, the particle diameter of particle is 7.1nm, relative standard deviation is 7%.
Embodiment 3
(1) deionized water of 3mL is added drop-wise in 17mL absolute ethyl alcohol, stirs, be placed in 100mLIn polytetrafluoroethylliner liner;
(2) 1.8mL butyl titanate is added to 9.5mL oleic acid, 6.5mL oleyl amine, 6.0mL absolute ethyl alcoholIn mixed system, stir, obtain light yellow transparent solution, be placed in 40mL polytetrafluoroethylliner liner;
(3) 40mL polytetrafluoroethylliner liner is inserted in 100mL polytetrafluoroethylliner liner, is then placed in anti-Answer in still 180 DEG C of reactions 9 hours;
(4) after completion of the reaction,, by the white emulsion centrifugation obtaining, precipitation is dispersed in to 50mL ringIn hexane, reflux 4 hours in 80 DEG C;
(5) the mixed solution washing precipitate of use cyclohexane and ethanol, in the mixed solution of cyclohexane and ethanol,The volume ratio of cyclohexane and ethanol is 1:8, then uses deionized water washing sediment. Sediment is freezing in-70 DEG CBe dried, obtain the Detitanium-ore-type TiO of size distribution homogeneous2Monocrystal material.
The prepared TiO of the present embodiment2Monocrystal material comprises a large amount of pattern rules, size uniform, good dispersionNano particle, the particle diameter of particle is 7.0nm, relative standard deviation is 8%.
Embodiment 4
(1) deionized water of 5mL is added drop-wise in 15mL absolute ethyl alcohol, stirs, be placed in 100mLIn polytetrafluoroethylliner liner;
(2) 1.8mL butyl titanate is added to 9.5mL oleic acid, 6.5mL oleyl amine, 6.0mL absolute ethyl alcoholIn mixed system, stir, obtain light yellow transparent solution, be placed in 40mL polytetrafluoroethylliner liner;
(3) 40mL polytetrafluoroethylliner liner is inserted in 100mL polytetrafluoroethylliner liner, is then placed in anti-Answer in still 180 DEG C of reactions 9 hours;
(4) after completion of the reaction,, by the white emulsion centrifugation obtaining, precipitation is dispersed in to 50mL ringIn hexane, reflux 2 hours in 80 DEG C;
(5) use the mixed solution washing precipitate of cyclohexane and ethanol, then use deionized water washing sediment.Sediment, in-70 DEG C of freeze dryings, is obtained to the Detitanium-ore-type TiO of size distribution homogeneous2Monocrystal material.
The prepared TiO of the present embodiment2Monocrystal material comprises a large amount of pattern rules, size uniform, good dispersionNano particle, the particle diameter of particle is 7.1nm, relative standard deviation is 7%.
Embodiment 5
The present embodiment is TiO prepared by the embodiment of the present invention 12Monocrystal material (B) is as catalyst and commercially availableThe commercial average grain diameter TiO that is 7nm2(A) (Relative Size standard deviation approximately 25%) catalyst existsPhotocatalysis effect contrast when degradation of dye methylene blue.
0.01g catalyst is added in the methylene blue solution that 100mL contains 10mg/L, under lucifuge condition, stirsMix 1h, make to arrive between catalyst and dyestuff adsorption-desorption balance. The high pressure xenon that is 365nm with emission wavelengthLamp is from external irradiation reactor. In During Illumination, every 15min sampling, the centrifugal 5min of 8000r/min,Get supernatant liquid tests in ultraviolet-uisible spectrophotometer. The concentration of methylene blue solution corresponding toThe absorbance at 665nm place. Result (as Fig. 3) shows, the TiO preparing with the present invention2Material catalytic degradationThe specific activity commercialization TiO of methylene blue2The activity of catalyst is high.
Applicant's statement, the present invention illustrates method detailed of the present invention by above-described embodiment, but the present inventionBe not limited to above-mentioned method detailed, do not mean that the present invention must rely on above-mentioned method detailed and could implement.Person of ordinary skill in the field should understand, any improvement in the present invention is each former to product of the present inventionThe selections of the equivalence replacement of material and the interpolation of auxiliary element, concrete mode etc., all drop on protection model of the present inventionWithin enclosing and disclosing scope.
Claims (10)
1. a nano-TiO2Monocrystal material, is characterized in that, described nano-TiO2Monocrystal material granularity is dividedCloth homogeneous, average grain diameter is 7nm, relative standard deviation is below 9%.
2. a nano-TiO as claimed in claim 12The preparation method of monocrystal material, is characterized in that,Said method comprising the steps of:
(1) deionized water of 1～7 parts by volume is mixed with the ethanol of 19～13 parts by volume, stir evenly, obtain waterAlcoholic solution, proceeds in inner bag, and water-alcohol solution accounts for 14～26% of reactor inner bag volume;
(2) butyl titanate of 1.8 parts by volume is joined by the oleic acid of 9.5 parts by volume, the oil of 6.5 parts by volumeIn the mixed system of the ethanol composition of amine and 6.0 parts by volume, obtain mixed solution, proceed in inner bag;
(3) the described inner bag of step (2) is inserted in the described inner bag of step (1), wherein, step (2)The ratio of the volume of the described inner bag of the volume of described inner bag and step (1) is 2:5, carries out hydro-thermal reaction, obtainsNano-TiO2Monocrystal material.
3. method according to claim 2, is characterized in that, in the described water-alcohol solution of step (1),The consumption of deionized water is 2～5 parts by volume; The consumption of ethanol is preferably 18～15 parts by volume;
Preferably, in the described water-alcohol solution of step (1), the volume ratio of deionized water and ethanol is (2～5):(18～15)。
4. according to the method in claim 2 or 3, it is characterized in that hydro-thermal reaction in step (3)Time be 6～18 hours;
Preferably, the temperature of hydro-thermal reaction is 180～200 DEG C.
5. according to the method described in claim 2-4 any one, it is characterized in that, described method is also included inAfter reaction finishes, carry out successively step (4) and step (5), wherein, step (4) is: by step (3)The product that hydro-thermal reaction obtains is centrifugal, and the centrifugal precipitation obtaining is dispersed in cyclohexane and is refluxed; Step (5)The sediment obtaining for washing step (4), and freeze drying.
6. according to the method described in claim 2-5 any one, it is characterized in that, step (4) is described returnsThe temperature of stream is 60～80 DEG C, and the time of backflow is preferably 2～6 hours.
7. according to the method described in claim 5 or 6, it is characterized in that, the washing in step (5) is excellentElect as first and to wash with cyclohexane and the mixed solution of ethanol, then wash by deionized water;
Preferably, in the mixed solution of cyclohexane and ethanol, the volume ratio of cyclohexane and ethanol is 1:8.
8. according to the method described in claim 5-7 any one, it is characterized in that, freezing in step (5)Dry temperature is-75～-50 DEG C.
9. according to the method described in claim 2-8 any one, it is characterized in that, described method comprises followingStep:
(1) deionized water of 2～5 parts by volume is mixed with the ethanol of 18～15 parts by volume, stir evenly, obtain waterAlcoholic solution, proceeds in inner bag, and water-alcohol solution accounts for 17～23% of reactor inner bag volume;
(2) butyl titanate of 1.8 parts by volume is joined by the oleic acid of 9.5 parts by volume, the oil of 6.5 parts by volumeIn the mixed system of the ethanol composition of amine and 6.0 parts by volume, obtain mixed solution, proceed in inner bag;
(3) the described inner bag of step (2) is inserted in the described inner bag of step (1), wherein, step (2)The ratio of the volume of the described inner bag of the volume of described inner bag and step (1) is 2:5,180～200 DEG C of hydro-thermal reactions6～18h, obtains nano-TiO2Monocrystal material;
(4) product step (3) hydro-thermal reaction being obtained is centrifugal, and the centrifugal precipitation obtaining is dispersed in to ringIn hexane, reflux;
(5) sediment that washing step (4) obtains, and freeze drying, obtain TiO2Monocrystal material.
10. a nano-TiO as claimed in claim 12Monocrystal material is as the purposes of photochemical catalyst.
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