CN104386743B - A kind of Detitanium-ore-type TiO 2the solvothermal preparation method of nanotube - Google Patents

A kind of Detitanium-ore-type TiO 2the solvothermal preparation method of nanotube Download PDF

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CN104386743B
CN104386743B CN201410688295.6A CN201410688295A CN104386743B CN 104386743 B CN104386743 B CN 104386743B CN 201410688295 A CN201410688295 A CN 201410688295A CN 104386743 B CN104386743 B CN 104386743B
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nanotube
ore
detitanium
tio
acetic acid
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CN104386743A (en
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杨伟光
胡雅静
唐颖
王亚丽
朱琳彦
王晨
黄璐
史伟民
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University of Shanghai for Science and Technology
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G23/00—Compounds of titanium
    • C01G23/04—Oxides; Hydroxides
    • C01G23/047—Titanium dioxide
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
    • C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/01—Particle morphology depicted by an image
    • C01P2004/03—Particle morphology depicted by an image obtained by SEM
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/10—Particle morphology extending in one dimension, e.g. needle-like
    • C01P2004/13—Nanotubes

Abstract

The invention belongs to field of nanometer material technology, relate to a kind of Detitanium-ore-type TiO 2the solvothermal preparation method of nanotube.Its preparation technology's flow process is: take glacial acetic acid as solvent, TiF 4for titanium source, F127(segmented copolymer, polyoxyethylene-poly-oxypropylene polyoxyethylene) as tensio-active agent, prepare unformed TiO by solvent-thermal method 2nanotube, obtains anatase titanium dioxide TiO after Overheating Treatment 2nanotube.Wherein, glacial acetic acid consumption is 10-50mL, TiF 4consumption is 50-150mg, F127 consumption is 1-5g, and temperature of reaction is 160-200 DEG C, and soaking time is 12-48h, and thermal treatment temp is 450-550 DEG C, and heat treatment time is 1-3h.A kind of Detitanium-ore-type TiO provided by the present invention 2the solvothermal preparation method of nanotube, synthesis step is simple, and cost is lower, does not use strong base solution, is applicable to extensive synthesis.

Description

A kind of Detitanium-ore-type TiO 2the solvothermal preparation method of nanotube
Technical field
Belong to field of nanometer material technology, relate to a kind of Detitanium-ore-type TiO 2the solvothermal preparation method of nanotube.
Background technology
Dye sensitization solar battery (DSSC), compared with crystalline semiconductor solar cell, because it has the advantages such as with low cost, environmental friendliness, manufacture craft are simple, and receives the extensive concern of investigator.TiO 2as the ideal material of dye-sensitized solar cell anode, the photoelectric transformation efficiency of its microscopic appearance to battery has important influence.TiO 2nanotube has larger specific surface area and electron propagation ducts at a high speed, it can be used as the light anode of dye sensitization solar battery to be conducive to improving the photoelectric transformation efficiency of battery.
At present, the TiO that reported of document 2the preparation method of nanotube mainly contains anonizing, hydrothermal method and template.Anonizing adopts electrochemical method, using highly purified Ti sheet as work anode, obtains TiO at fluorine-containing electrolyte solution after anodic oxidation 2nanotube.Such as, Wan Bin etc. are with pure Ti sheet for anode, and Pt sheet is to electrode, and electrolytic solution adopts 0.5wt%HF and 1mol/L (NH 4) H 2pO 3solution, after 20V anodic oxidation 15h, it is main TiO that the 1h that anneals under the air atmosphere of 500 DEG C obtains anatase structured 2nano-tube film.(ten thousand is refined, etc., TiO is prepared in anodic oxidation 2nanotube and photocatalysis performance thereof, chemical journal, 2008,6 (11): 1301-1306).Hydrothermal method utilizes water as reaction medium, normally by TiO 2(P25 type) mixes with the NaOH solution (10mol/L) of high density and carries out hydro-thermal reaction, then obtains TiO through overpickling and high-temperature calcination 2nanotube.Such as, Yu etc. are by the TiO of 0.5g 2nano particle joins 18mL10mol × L -1naOH solution in, proceeded to after magnetic agitation 30min in the water heating kettle of 25mL and carried out hydro-thermal reaction, in the HCl washing of 110 DEG C of reactions 20h, the white precipitate 0.1mol/L be obtained by reacting for several times to remove Na +, finally use deionized water by 70 DEG C of dryings in atmosphere after washing of precipitate for several times.（Y.Yu,P.Zhang,L.Guo,etal,TheDesignofTiO 2Nanostructures(Nanoparticle,Nanotube,andNanosheet)andTheirPhotocatalyticActivity[J],J.Phys.Chem.C,2014,118:12727-12733）。Template uses anodised aluminium (AAO) etc. as template, then obtain TiO by methods such as sol-gel, liquid phase or vapour depositions 2nanotube.Such as, obtained AAO template is immersed in concentration by Wang Jinshu etc. is 0.1mol × L -11L (NH 4) 2tiF 6in solution, at 40 DEG C, after constant temperature deposition 10min, AAO template is placed in air drying 30min, finally at 400 DEG C, thermal treatment 4h obtains TiO 2nanotube.(Cui Yuntao, Wang Jinshu, Li Hongyi, etc., AAO template on the impact of liquid deposition TiO2 nano array structure, Chinese Journal of Inorganic Chemistry, 2009,25 (7): 1274-1278).
In sum, all there is respective weak point in current used method, and such as, anonizing needs high purity Ti sheet cost higher, and the method is not easy to big area preparation; Hydro-thermal rule needs the alkaline solution using high density, and needs multi step strategy just can obtain TiO 2nanotube; Template easily makes TiO in the process removing template 2nanotube is contaminated, and the process removed can cause caving in of nano tube structure.Therefore, with low cost, building-up process is simple, does not need to use the method for high density strong base solution to need to develop further.Solvent-thermal method used in the present invention prepares Detitanium-ore-type TiO 2nanotube have not been reported, and compares with template with anonizing, hydrothermal method, and synthesis step is simple, and cost is lower, does not need to use strong base solution, is easy to extensive synthesis, has practical value.
Summary of the invention
The object of this invention is to provide a kind of Detitanium-ore-type TiO 2the solvothermal preparation method of nanotube, present method synthesis step is simple, and cost is lower, does not use strong base solution, is applicable to extensive synthesis.
For achieving the above object, preparation method's specific embodiments proposed by the invention is as described below:
A. measure 10-50ml glacial acetic acid to add after in beaker, then weigh 1-5gF127(segmented copolymer, polyoxyethylene-poly-oxypropylene polyoxyethylene) pour in glacial acetic acid, stir to clarify;
B. 50-150mgTiF is taken 4in beaker in steps A, continue to stir to clarify;
C. the settled solution obtained in step B is added in water heating kettle, put into baking oven after being sealed by water heating kettle, control temperature of reaction 160-200 DEG C, insulation 12-48h;
D., after reaction terminates, treat that water heating kettle naturally cools to room temperature, obtained precipitation dehydrated alcohol and water are respectively washed three times, after centrifugation, precipitation is put into the oven dry of 60 DEG C, loft drier;
E. the throw out of oven dry is obtained Detitanium-ore-type TiO at 450-550 DEG C of thermal treatment 1-3h 2nanotube.
The above-mentioned TiO prepared 2nanotube, characterizing its thing through XRD is pure Detitanium-ore-type TiO mutually 2, there is (see figure 1) without other dephasign, this TiO 2nanotube caliber is about 450nm, length 500nm to several microns of (see figure 2)s.
The Detitanium-ore-type TiO that the present invention prepares 2nanotube can be used as the light anode material of dye sensitization solar battery, and it has larger specific surface area and electron propagation ducts at a high speed, will be conducive to the photoelectric transformation efficiency improving battery.
Accompanying drawing explanation
Fig. 1 is the Detitanium-ore-type TiO of preparation in embodiment one 2the XRD figure of nanotube.
Fig. 2 is the Detitanium-ore-type TiO of preparation in embodiment one 2the SEM figure of nanotube.
Embodiment
Below in conjunction with embodiment, the present invention is described in detail:
Embodiment one
A. measure 20ml glacial acetic acid to add after in beaker, then weigh 2gF127 and pour in glacial acetic acid, stir to clarify;
B. 100mgTiF is taken 4in beaker in steps A, continue to stir to clarify;
C. the settled solution obtained in step B is added in water heating kettle, put into baking oven after being sealed by water heating kettle, control temperature of reaction 180 DEG C, insulation 24h;
D., after reaction terminates, treat that water heating kettle naturally cools to room temperature, obtained precipitation dehydrated alcohol and water are respectively washed three times, after centrifugation, precipitation is put into the oven dry of 60 DEG C, loft drier;
E. the throw out of oven dry is obtained Detitanium-ore-type TiO at 500 DEG C of thermal treatment 2h 2nanotube.
Embodiment two
A. measure 10ml glacial acetic acid to add after in beaker, then weigh 1gF127 and pour in glacial acetic acid, stir to clarify;
B. 50mgTiF is taken 4in beaker in steps A, continue to stir to clarify;
C. the settled solution obtained in step B is added in water heating kettle, put into baking oven after being sealed by water heating kettle, control temperature of reaction 200 DEG C, insulation 12h;
D., after reaction terminates, treat that water heating kettle naturally cools to room temperature, obtained precipitation dehydrated alcohol and water are respectively washed three times, after centrifugation, precipitation is put into the oven dry of 60 DEG C, loft drier;
E. the throw out of oven dry is obtained Detitanium-ore-type TiO at 450 DEG C of thermal treatment 3h 2nanotube.
Embodiment three
A. measure 50ml glacial acetic acid to add after in beaker, then weigh 5gF127 and pour in glacial acetic acid, stir to clarify;
B. 150mgTiF is taken 4in beaker in steps A, continue to stir to clarify;
C. the settled solution obtained in step B is added in water heating kettle, put into baking oven after being sealed by water heating kettle, control temperature of reaction 160 DEG C, insulation 48h;
D., after reaction terminates, treat that water heating kettle naturally cools to room temperature, obtained precipitation dehydrated alcohol and water are respectively washed three times, after centrifugation, precipitation is put into the oven dry of 60 DEG C, loft drier;
E. the throw out of oven dry is obtained Detitanium-ore-type TiO at 550 DEG C of thermal treatment 1h 2nanotube.

Claims (1)

1. a solvothermal preparation method for anatase titania nanotube, is characterized in that the concrete steps of the method are:
A. measure 10-50ml glacial acetic acid to add after in beaker, then weigh 1-5gF127(segmented copolymer, polyoxyethylene-poly-oxypropylene polyoxyethylene) pour in glacial acetic acid, stir to clarify;
B. 50-150mgTiF is taken 4in beaker in step a, continue to stir to clarify;
C. the settled solution obtained in step b is added in water heating kettle, put into baking oven after being sealed by water heating kettle, control temperature of reaction 160-200 DEG C, insulation 12-48h;
D., after reaction terminates, treat that water heating kettle naturally cools to room temperature, obtained precipitation dehydrated alcohol and water are respectively washed three times, after centrifugation, precipitation is put into the oven dry of 60 DEG C, loft drier;
E. the throw out of oven dry is obtained Detitanium-ore-type TiO at 450-550 DEG C of thermal treatment 1-3h 2nanotube.
CN201410688295.6A 2014-11-26 2014-11-26 A kind of Detitanium-ore-type TiO 2the solvothermal preparation method of nanotube Active CN104386743B (en)

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CN104891567B (en) * 2015-06-24 2017-03-01 齐鲁工业大学 Tubulose TiO2The preparation method of/redox graphene composite
CN105390677A (en) * 2015-11-02 2016-03-09 吉林大学 Carbon self-coated semiconductor metal oxide nanosheet and graphene composite material and application thereof
CN106430303B (en) * 2016-09-12 2017-12-05 齐鲁工业大学 A kind of classification titanium dioxide of mixed structure and preparation method thereof

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2006044992A (en) * 2004-08-04 2006-02-16 National Institute Of Advanced Industrial & Technology Simple method for manufacturing titanium oxide nanotube structure and titanium oxide nanotube structure obtained by the same method
CN101182033A (en) * 2007-11-20 2008-05-21 中国科学院广州能源研究所 Method for preparing titanium dioxide nano-tube
CN101817552A (en) * 2010-03-25 2010-09-01 山东大学 Titanium dioxide micron tube material and preparation method thereof
CN103288126A (en) * 2013-05-14 2013-09-11 哈尔滨工程大学 Method of preparing titanium dioxide nanotube with assistance of cationic surface active agent
CN103466695A (en) * 2013-08-23 2013-12-25 中山大学 Method for preparing titanium dioxide submicron tube with high specific surface area
KR101447206B1 (en) * 2013-03-08 2014-10-06 인하대학교 산학협력단 The manufacturing method of titanium dioxide nanotubes

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2006044992A (en) * 2004-08-04 2006-02-16 National Institute Of Advanced Industrial & Technology Simple method for manufacturing titanium oxide nanotube structure and titanium oxide nanotube structure obtained by the same method
CN101182033A (en) * 2007-11-20 2008-05-21 中国科学院广州能源研究所 Method for preparing titanium dioxide nano-tube
CN101817552A (en) * 2010-03-25 2010-09-01 山东大学 Titanium dioxide micron tube material and preparation method thereof
KR101447206B1 (en) * 2013-03-08 2014-10-06 인하대학교 산학협력단 The manufacturing method of titanium dioxide nanotubes
CN103288126A (en) * 2013-05-14 2013-09-11 哈尔滨工程大学 Method of preparing titanium dioxide nanotube with assistance of cationic surface active agent
CN103466695A (en) * 2013-08-23 2013-12-25 中山大学 Method for preparing titanium dioxide submicron tube with high specific surface area

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