CN105506736A - Nano TiO2 single-crystal material, preparation method and application of material - Google Patents
Nano TiO2 single-crystal material, preparation method and application of material Download PDFInfo
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- CN105506736A CN105506736A CN201510971261.2A CN201510971261A CN105506736A CN 105506736 A CN105506736 A CN 105506736A CN 201510971261 A CN201510971261 A CN 201510971261A CN 105506736 A CN105506736 A CN 105506736A
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- 239000000463 material Substances 0.000 title claims abstract description 46
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title abstract description 24
- 239000013078 crystal Substances 0.000 title abstract description 8
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 22
- QGLWBTPVKHMVHM-KTKRTIGZSA-N (z)-octadec-9-en-1-amine Chemical compound CCCCCCCC\C=C/CCCCCCCCN QGLWBTPVKHMVHM-KTKRTIGZSA-N 0.000 claims abstract description 19
- 238000006243 chemical reaction Methods 0.000 claims abstract description 19
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 claims abstract description 15
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 claims abstract description 15
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 claims abstract description 15
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000005642 Oleic acid Substances 0.000 claims abstract description 15
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 claims abstract description 15
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 claims abstract description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 65
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 29
- 238000000034 method Methods 0.000 claims description 26
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 20
- 238000005406 washing Methods 0.000 claims description 18
- 239000008367 deionised water Substances 0.000 claims description 16
- 229910021641 deionized water Inorganic materials 0.000 claims description 16
- 238000002156 mixing Methods 0.000 claims description 16
- 238000003756 stirring Methods 0.000 claims description 15
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 11
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 11
- 238000009826 distribution Methods 0.000 claims description 11
- 238000001556 precipitation Methods 0.000 claims description 11
- 238000010992 reflux Methods 0.000 claims description 5
- 239000011941 photocatalyst Substances 0.000 claims description 2
- 239000002245 particle Substances 0.000 abstract description 27
- 230000001699 photocatalysis Effects 0.000 abstract description 6
- 239000000654 additive Substances 0.000 abstract description 3
- 239000000203 mixture Substances 0.000 abstract description 3
- 238000005265 energy consumption Methods 0.000 abstract description 2
- 239000002086 nanomaterial Substances 0.000 abstract description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 34
- 239000000243 solution Substances 0.000 description 29
- 229960004756 ethanol Drugs 0.000 description 18
- 229960000935 dehydrated alcohol Drugs 0.000 description 12
- 239000002105 nanoparticle Substances 0.000 description 7
- 239000002244 precipitate Substances 0.000 description 7
- 239000000839 emulsion Substances 0.000 description 6
- 239000013049 sediment Substances 0.000 description 6
- 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 5
- 238000005119 centrifugation Methods 0.000 description 5
- 229960000907 methylthioninium chloride Drugs 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- 238000006460 hydrolysis reaction Methods 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 3
- 230000015556 catabolic process Effects 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 238000006731 degradation reaction Methods 0.000 description 3
- 230000007062 hydrolysis Effects 0.000 description 3
- 238000007146 photocatalysis 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
- 230000000996 additive effect Effects 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 239000000975 dye Substances 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
- 235000021122 unsaturated fatty acids Nutrition 0.000 description 2
- 150000004670 unsaturated fatty acids Chemical class 0.000 description 2
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000006136 alcoholysis reaction Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000007073 chemical hydrolysis Effects 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
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 239000000976 ink Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000000593 microemulsion method Methods 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000012716 precipitator Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000005070 sampling Methods 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
- 238000003786 synthesis reaction Methods 0.000 description 1
- -1 titanic acid ester Chemical class 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
-
- 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
-
- B01J35/39—
-
- B01J35/647—
-
- 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 relates to a nano TiO2 single-crystal material, a preparation method and an application of the material. A double-layer reaction kettle liner is adopted for a hydrothermal reaction, oleic acid and oleylamine are adopted as additives, the composition and the adding amount of a water-alcohol solution are controlled, adding amounts of the oleic acid and the oleylamine are controlled, anatase type nano TiO2 single-crystal particles with the uniform size and good crystallinity are prepared, the average particle size is 9 nm, and the relative standard deviation is below 8%. The prepared nano TiO2 has regular morphology, high product purity, good dispersibility and higher photocatalytic activity, the preparation method of the nano TiO2 single-crystal material is simple to operate and environment-friendly, the reaction condition is mild, energy consumption is low, consumed time is short, and popularization and use are easy.
Description
Technical field
The invention belongs to technical field of nano material, relate to a kind of nano-TiO
2monocrystal material, preparation method and its usage, particularly relate to a kind of nano-TiO with highly homogeneous granularity
2monocrystal material, preparation method, and it is in the purposes of photocatalysis field.
Background technology
TiO
2the traditional industry fields such as pigment, coating, ink, makeup and environmental pollution improvement are widely used in the physical and chemical performance of its excellence.Particularly the photochemical catalysis of its excellence and photoelectric properties, make TiO
2a large amount of application is also obtain in the new industry such as photochemical catalysis and solar cell.TiO
2these application have close contacting with himself pattern, size and crystalline structure etc.TiO
2there is the crystal formation that brookite, anatase octahedrite and rutile three kinds is common, wherein anatase octahedrite TiO
2excellent performance is shown in photochemical catalysis and solar cell etc.The TiO that size is little
2have larger specific surface area, high-specific surface area contributes to improving the absorption to light and specific refractory power, is conducive to the absorption of reactant on surface, makes TiO
2there is higher photocatalytic activity; For ensureing TiO
2stable performance in the research and apply continued, the TiO of synthesis
2material should have crystalline structure, and particle scale should keep homogeneous; Meanwhile, the nano-TiO that size-grade distribution is homogeneous
2in metering and field fo standardization, there is very important application.Therefore, the anatase crystal nano TiO 2 material that prepared sizes are homogeneous has great importance.
At present, nano-TiO
2the preparation method of material mainly contains chemical hydrolysis, hydrothermal method, alcoholysis method, the precipitator method, sol-gel method and microemulsion method etc., and wherein, hydrothermal method is a kind of common method.Hydrothermal method is in autoclave reactor, adopts the aqueous solution as reaction medium, is heated, create a high-temperature high-voltage reaction environment, presoma is reacted by reaction vessel.Hydrothermal method directly can obtain the powder of well-crystallized, does not need to do pyroprocessing, avoids the powder hard aggregation that may be formed in the process, and by changing processing condition, can realize the control to the characteristic such as diameter of particle, crystal formation, meanwhile, obtained powder purity is high.
CN103964502A discloses a kind of nano-TiO
2monocrystal material and its production and use, it utilizes collosol and gel to combine with hydrothermal synthesis method, first obtain gel in stirring at room temperature, then the white precipitate obtained gel centrifugal is distributed to 120 ~ 150 DEG C of hydro-thermals in water alcohol system, obtain the nano-TiO of particle diameter at 10 ~ 15nm
2material, but prepare nano-TiO by the method
2needing first titanic acid ester to be added drop-wise in the system of water and dehydrated alcohol, leaving standstill to forming gel, this standing process time is long, and length consuming time is unfavorable for large-scale promotion.Therefore, be necessary that research one saves time, prepares nano-TiO easily
2the method of material.
Summary of the invention
The object of this invention is to provide a kind of particle diameter is 9nm, relative standard deviation below 8%, the anatase type nano TiO that size-grade distribution is homogeneous
2monocrystal material, preparation method and its usage.
First aspect, the invention provides a kind of nano-TiO
2monocrystal material, described nano-TiO
2material is Detitanium-ore-type TiO
2, size-grade distribution is homogeneous, and median size is 9nm, relative standard deviation is below 8%, relative standard deviation such as can be 8%, 7.5%, 7%, 6.5%, 6%, 5%, 4%, 3%, 2.8%, 2%, 1% or 0 etc., known by this statement, nano-TiO of the present invention
2particle diameter between 9 × (1-8%)=8.28nm to 9 × (1+8%)=9.72nm, any other statement but actual particle size drops between 8.28nm to 9.72nm, also belong to protection scope of the present invention.Illustrate: particle diameter is 8.9nm, relative standard deviation is 6.8%, and particle size range of its representative is actually 8.2948nm to 9.5052nm, within the scope having dropped on 8.28nm to 9.72nm of the present invention, thus also belongs to protection scope of the present invention.
Second aspect, the invention provides a kind of nano-TiO prepared described in first aspect
2the method of monocrystal material, comprises the following steps:
(1) mixed by the ethanol of the deionized water of 2 parts by volume with 18 parts by volume, stir evenly, obtain water-alcohol solution, proceed in inner bag, water-alcohol solution accounts for 20% of reactor inner bag volume;
(2) butyl (tetra) titanate of 1.8 parts by volume is joined in the mixed system be made up of the oleyl amine of the oleic acid of 8.5 parts by volume, 6 ~ 8 parts by volume and the ethanol of 6 parts by volume, obtain mixing solutions, proceed in inner bag;
(3) step (2) described inner bag is inserted in step (1) described inner bag, wherein, the ratio of the volume of step (2) described inner bag and the volume of step (1) described inner bag is 2:5, carries out hydro-thermal reaction, obtains nano-TiO
2monocrystal material.
The present invention adopts double-deck reactor inner bag to carry out hydro-thermal reaction, using oleic acid and oleyl amine as additive, and controls composition and the addition of water-alcohol solution, regulates the addition of oleic acid and oleyl amine, regulation and control nano-TiO
2the pattern of material and size.Unsaturated fatty acids pinolenic acid and unsaturated amine oleyl amine can reduce the hydrolysis rate of butyl (tetra) titanate in hydro-thermal reaction, and then affect nano-TiO
2particle diameter, simultaneously, the present invention adopts double-deck reactor inner bag to carry out hydro-thermal reaction, and the water-alcohol solution in outer field reactor inner bag manufactures the reaction environment of water alcohol steam in hydrothermal reaction process, can regulate the nano-TiO that the hydrolysis rate of butyl (tetra) titanate and regulation and control generate equally
2particle diameter.
Ethanol of the present invention is dehydrated alcohol.
Inner bag of the present invention is reactor inner bag, is preferably polytetrafluoroethylliner liner.
Preferably, in step (2), the consumption of oleyl amine is 6 ~ 8 parts by volume, such as can be 6 parts by volume, 6.2 parts by volume, 6.5 parts by volume, 6.7 parts by volume, 7 parts by volume, 7.3 parts by volume, 7.6 parts by volume, 7.8 parts by volume or 8 parts by volume etc., be preferably 6.5 ~ 7 parts by volume.
In the present invention, the ratio of the volume of step (2) described inner bag and the volume of step (1) described inner bag is 2:5, illustrate, the volume of step (2) described inner bag is 40mL, and the volume of step (1) described inner bag is 100mL.Or the volume of step (2) described inner bag is 200mL, and the volume of step (1) described inner bag is 500mL.In the present invention, the volume of step (2) described inner bag and step (1) described inner bag is without concrete restriction, as long as the ratio that can meet the volume of step (2) described inner bag and the volume of step (1) described inner bag is 2:5, those skilled in the art can select as required, and the consumption of each component in the consumption of water-alcohol solution and step (2) in determining step (1) ordinatedly, " ordinatedly " after referring to that the volume of step (1) described inner bag is determined, the standard that the consumption of water-alcohol solution accounts for 14 ~ 26% of the described inner bag volume of step (1) according to water-alcohol solution uses, contrary, the consumption of water-alcohol solution also will according to same standard to select the volume of step (1) described inner bag after determining.
Preferably, the time of step (3) described hydro-thermal reaction is 4 ~ 18h, such as, can be 4h, 4.5h, 4.8h, 5h, 5.6h, 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, such as, 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 also comprises carries out step (4) and step (5) after the completion of reaction successively, wherein, step (4) is: white emulsion step (3) hydro-thermal reaction obtained is centrifugal, the centrifugal precipitation obtained is dispersed in hexanaphthene and refluxes; Step (5) is: the throw out that washing step (4) obtains, and lyophilize.
Preferably, the centrifugal precipitation obtained is dispersed in the hexanaphthene of 50 parts by volume and refluxes, the temperature of backflow is preferably 60 ~ 80 DEG C, such as can be 60 DEG C, 62 DEG C, 65 DEG C, 70 DEG C, 75 DEG C, 78 DEG C or 80 DEG C etc., the time of backflow is preferably 2 ~ 4h, and the time of backflow such as can be 2h, 2.5h, 3h, 3.2h or 4h etc.
It is remove unreacted oleic acid and oleyl amine that the centrifugal precipitation obtained is distributed to the object refluxed in hexanaphthene by the present invention, because unsaturated fatty acids pinolenic acid and unsaturated amine oleyl amine are as the polymer substance of long-chain, be difficult to remove clean by the washing of routine, therefore precipitation to be distributed in hexanaphthene and to carry out reflux operation by the present invention.
Preferably, washing in step (5) is the mixing solutions washing precipitate first using hexanaphthene and ethanol, use deionized water washing sediment again, washed by the mixing solutions of continuation hexanaphthene and ethanol upon reflowing and use deionized water wash further, can obtain that purity is high, the nano-TiO of good dispersity
2material.
Preferably, in the mixing solutions of described hexanaphthene and ethanol, the volume ratio of hexanaphthene and ethanol is 1:9.
Preferably, in step (5), cryodesiccated temperature is-75 ~-50 DEG C, such as, 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 to refer between various reactant proportionlity by volume, and the measure unit of parts by volume does not limit, and can be any volume metering units such as mL or L.
In the third aspect, the invention provides a kind of nano-TiO as described in relation to the first aspect
2monocrystal material is as the purposes of photocatalyst.
Compared with prior art, beneficial effect of the present invention is as follows:
(1) the present invention is using oleic acid and oleyl amine as additive, and regulates the addition of oleic acid and oleyl amine, regulates the hydrolysis rate of butyl (tetra) titanate, and then regulation and control nano-TiO
2the pattern of material and size, meanwhile, the present invention adopts double-deck reactor inner bag to carry out hydro-thermal reaction, and the water-alcohol solution in outer field reactor inner bag manufactures the reaction environment of water alcohol steam in hydrothermal reaction process, control composition and the addition of water-alcohol solution, and then the nano-TiO that regulation and control generate
2particle diameter.Adopt the TiO that method of the present invention obtains
2granule-morphology rule, better crystallinity degree, size are even, and particle diameter is 7nm, relative standard deviation below 9%, good dispersity and product purity is high, and there is higher photocatalytic activity;
(2) simple to operate, the environmental friendliness of preparation method of the present invention, reaction conditions is gentle, energy consumption is low, consuming time short, is easy to promote the use of.
Accompanying drawing explanation
Fig. 1 is the TiO that the embodiment of the present invention 1 obtains
2the transmission electron microscope picture of monocrystal material;
Fig. 2 is the TiO that the embodiment of the present invention 1 obtains
2the XRD figure of monocrystal material;
Fig. 3 is the nano-TiO that the embodiment of the present invention 1 obtains
2monocrystal material (B) and commercially available commercialization nano-TiO
2material (A) degradation of methylene blue photocatalysis effect comparison diagram.
Embodiment
Technical scheme of the present invention is further illustrated by embodiment below in conjunction with accompanying drawing.
Embodiment 1
(1) deionized water of 2mL is added drop-wise in 18mL dehydrated alcohol, stirs, be placed in 100mL polytetrafluoroethylliner liner;
(2) 1.8mL butyl (tetra) titanate is added in the mixed system of 8.5mL oleic acid, 6.5mL oleyl amine, 6.0mL dehydrated alcohol, stirs, 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 reactor 200 DEG C reaction 18 hours;
(4) after completion of the reaction, by the white emulsion centrifugation obtained, precipitation is dispersed in 50mL hexanaphthene in 80 DEG C of backflows 6 hours;
(5) use the mixing solutions washing precipitate of hexanaphthene and ethanol, in the mixing solutions of hexanaphthene and ethanol, the volume ratio of hexanaphthene and ethanol is 1:9, then uses deionized water washing sediment.By throw out in-75 DEG C of lyophilizes, namely obtain the Detitanium-ore-type TiO that size-grade distribution is homogeneous
2monocrystal material.
TiO obtained by the present embodiment
2monocrystal material comprises the nano particle of a large amount of pattern rule, size uniform, good dispersity, and the particle diameter of particle is 9.0nm, and relative standard deviation is 8%.
As can be seen from the transmission electron microscope shown in Fig. 1, Titanium dioxide nanoparticle even particle size distribution prepared by the present invention, good dispersity.Through the statistics of more than 500 particles, its size distribution is about 9.0 ± 0.7nm.
XRD figure shown in Fig. 2 shows, and wherein the different crystal faces of the corresponding anatase-type titanium oxide of position difference at 5 peaks, therefore show that titania meterial prepared by the present invention is Detitanium-ore-type.
Embodiment 2
(1) deionized water of 2mL is added drop-wise in 18mL dehydrated alcohol, stirs, be placed in 100mL polytetrafluoroethylliner liner;
(2) 1.8mL butyl (tetra) titanate is added in the mixed system of 8.5mL oleic acid, 6.5mL oleyl amine, 6.0mL dehydrated alcohol, stirs, 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 reactor 180 DEG C reaction 18 hours;
(4) after completion of the reaction, by the white emulsion centrifugation obtained, precipitation is dispersed in 50mL hexanaphthene in 80 DEG C of backflows 4 hours;
(5) use the mixing solutions washing precipitate of hexanaphthene and ethanol, in the mixing solutions of hexanaphthene and ethanol, the volume ratio of hexanaphthene and ethanol is 1:9, then uses deionized water washing sediment.By throw out in-70 DEG C of lyophilizes, namely obtain the Detitanium-ore-type TiO that size-grade distribution is homogeneous
2monocrystal material.
TiO obtained by the present embodiment
2monocrystal material comprises the nano particle of a large amount of pattern rule, size uniform, good dispersity, and the particle diameter of particle is 9.0nm, and relative standard deviation is 7%.
Embodiment 3
(1) deionized water of 2mL is added drop-wise in 18mL dehydrated alcohol, stirs, be placed in 100mL polytetrafluoroethylliner liner;
(2) 1.8mL butyl (tetra) titanate is added in the mixed system of 8.5mL oleic acid, 7.0mL oleyl amine, 6.0mL dehydrated alcohol, stirs, 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 reactor 180 DEG C reaction 9 hours;
(4) after completion of the reaction, by the white emulsion centrifugation obtained, precipitation is dispersed in 50mL hexanaphthene in 80 DEG C of backflows 3 hours;
(5) use the mixing solutions washing precipitate of hexanaphthene and ethanol, in the mixing solutions of hexanaphthene and ethanol, the volume ratio of hexanaphthene and ethanol is 1:9, then uses deionized water washing sediment.By throw out in-70 DEG C of lyophilizes, namely obtain the Detitanium-ore-type TiO that size-grade distribution is homogeneous
2monocrystal material.
TiO obtained by the present embodiment
2monocrystal material comprises the nano particle of a large amount of pattern rule, size uniform, good dispersity, and the particle diameter of particle is 9.1nm, and relative standard deviation is 6%.
Embodiment 4
(1) deionized water of 2mL is added drop-wise in 18mL dehydrated alcohol, stirs, be placed in 100mL polytetrafluoroethylliner liner;
(2) 1.8mL butyl (tetra) titanate is added in the mixed system of 8.5mL oleic acid, 7.0mL oleyl amine, 6.0mL dehydrated alcohol, stirs, 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 reactor 180 DEG C reaction 4 hours;
(4) after completion of the reaction, by the white emulsion centrifugation obtained, precipitation is dispersed in 50mL hexanaphthene in 80 DEG C of backflows 6 hours;
(5) use the mixing solutions washing precipitate of hexanaphthene and ethanol, then use deionized water washing sediment.By throw out in-70 DEG C of lyophilizes, namely obtain the Detitanium-ore-type TiO that size-grade distribution is homogeneous
2monocrystal material.
TiO obtained by the present embodiment
2monocrystal material comprises the nano particle of a large amount of pattern rule, size uniform, good dispersity, and the particle diameter of particle is 9.0nm, and relative standard deviation is 7%.
Embodiment 5
(1) deionized water of 2mL is added drop-wise in 18mL dehydrated alcohol, stirs, be placed in 100mL polytetrafluoroethylliner liner;
(2) 1.8mL butyl (tetra) titanate is added in the mixed system of 8.5mL oleic acid, 7.0mL oleyl amine, 6.0mL dehydrated alcohol, stirs, 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 reactor 180 DEG C reaction 9 hours;
(4) after completion of the reaction, by the white emulsion centrifugation obtained, precipitation is dispersed in 50mL hexanaphthene in 80 DEG C of backflows 2 hours;
(5) use the mixing solutions washing precipitate of hexanaphthene and ethanol, then use deionized water washing sediment.By throw out in-50 DEG C of lyophilizes, namely obtain the Detitanium-ore-type TiO that size-grade distribution is homogeneous
2monocrystal material.
TiO obtained by the present embodiment
2monocrystal material comprises the nano particle of a large amount of pattern rule, size uniform, good dispersity, and the particle diameter of particle is 9.1nm, and relative standard deviation is 6%.
Can find out that the proper extension reaction times is conducive to nano particle and fully grows by embodiment 4 and embodiment 5, particle diameter becomes large.
Embodiment 6
The present embodiment is TiO prepared by the embodiment of the present invention 1
2monocrystal material (B) is the TiO of 7nm as catalyzer and commercially available commercial median size
2(A) the photocatalysis effect contrast of (Relative Size standard deviation about 25%) catalyzer when degradation of dye methylene blue.
0.01g catalyzer is added to 100mL to be contained in the methylene blue solution of 10mg/L, stirs 1h under lucifuge condition, makes to arrive adsorption-desorption balance between catalyzer and dyestuff.Be that the high pressure xenon lamp of 365nm is from external irradiation reactor with emission wavelength.In During Illumination, every 15min sampling, the centrifugal 5min of 8000r/min, gets supernatant liquid and tests in ultraviolet-visible pectrophotometer.The concentration of methylene blue solution corresponds to the absorbancy at 665nm place.Result (as Fig. 3) shows, the TiO prepared with the present invention
2the specific activity commercialization TiO of material catalyzes degradation of methylene blue
2the activity of catalyzer is high.
Applicant states, the present invention illustrates method detailed of the present invention by above-described embodiment, but the present invention is not limited to above-mentioned method detailed, does not namely 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, to equivalence replacement and the interpolation of ancillary component, the concrete way choice etc. of each raw material of product of the present invention, all drops within protection scope of the present invention and open scope.
Claims (10)
1. a nano-TiO
2monocrystal material, is characterized in that, described nano-TiO
2monocrystal material size-grade distribution is homogeneous, and median size is 9nm, and relative standard deviation is below 8%.
2. a nano-TiO as claimed in claim 1
2the preparation method of monocrystal material, is characterized in that, said method comprising the steps of:
(1) mixed by the ethanol of the deionized water of 2 parts by volume with 18 parts by volume, stir evenly, obtain water-alcohol solution, proceed in inner bag, water-alcohol solution accounts for 20% of reactor inner bag volume;
(2) butyl (tetra) titanate of 1.8 parts by volume is joined in the mixed system be made up of the oleyl amine of the oleic acid of 8.5 parts by volume, 6 ~ 8 parts by volume and the ethanol of 6 parts by volume, obtain mixing solutions, proceed in inner bag;
(3) step (2) described inner bag is inserted in step (1) described inner bag, wherein, the ratio of the volume of step (2) described inner bag and the volume of step (1) described inner bag is 2:5, carries out hydro-thermal reaction, obtains nano-TiO
2monocrystal material.
3. method according to claim 2, is characterized in that, in step (2), oleyl amine consumption is preferably 6.5 ~ 7 parts by volume.
4. according to the method in claim 2 or 3, it is characterized in that, in step (3), the time of hydro-thermal reaction is 4 ~ 18 hours;
Preferably, the temperature of hydro-thermal reaction is 180 ~ 200 DEG C.
5. the method according to any one of claim 2-4, it is characterized in that, described method also comprises carries out step (4) and step (5) after the completion of reaction successively, wherein, step (4) is: product step (3) hydro-thermal reaction obtained is centrifugal, the centrifugal precipitation obtained is dispersed in hexanaphthene and refluxes; The throw out that step (5) obtains for washing step (4), and lyophilize.
6. the method according to any one of claim 2-5, is characterized in that, the temperature of step (4) described backflow is 60 ~ 80 DEG C, and the time of backflow is preferably 2 ~ 4 hours.
7. the method according to claim 5 or 6, is characterized in that, the washing in step (5) is preferably first washs with the mixing solutions of hexanaphthene and ethanol, then uses deionized water wash;
Preferably, in the mixing solutions of hexanaphthene and ethanol, the volume ratio of hexanaphthene and ethanol is 1:9.
8. the method according to any one of claim 5-7, is characterized in that, in step (5), cryodesiccated temperature is-75 ~-50 DEG C.
9. the method according to any one of claim 2-8, is characterized in that, said method comprising the steps of:
(1) mixed by the ethanol of the deionized water of 2 parts by volume with 18 parts by volume, stir evenly, obtain water-alcohol solution, proceed in inner bag, water-alcohol solution accounts for 20% of reactor inner bag volume;
(2) butyl (tetra) titanate of 1.8 parts by volume is joined in the mixed system be made up of the oleyl amine of the oleic acid of 8.5 parts by volume, 6.5 ~ 7 parts by volume and the ethanol of 6 parts by volume, obtain mixing solutions, proceed in inner bag;
(3) step (2) described inner bag is inserted in step (1) described inner bag, wherein, the ratio of the volume of step (2) described inner bag and the volume of step (1) described inner bag is 2:5, and 180 ~ 200 DEG C of hydro-thermal reaction 4 ~ 18h, obtain nano-TiO
2monocrystal material;
(4) product step (3) hydro-thermal reaction obtained is centrifugal, the centrifugal precipitation obtained is dispersed in hexanaphthene and refluxes;
(5) throw out that obtains of washing step (4), and lyophilize, obtain TiO
2monocrystal material.
10. a nano-TiO as claimed in claim 1
2monocrystal material is as the purposes of photocatalyst.
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