CN104386743A - Solvothermal preparation method of anatase type TiO2 nanometer tube - Google Patents

Abstract

The invention belongs to the field of a nanometer material and relates to a solvothermal preparation method of an anatase type TiO2 nanometer tube. The preparation method comprises the following technological steps: preparing an unformed TiO2 nanometer tube by a solvothermal method by taking glacial acetic acid as a solvent, TiF4 as a titanium source and F127 (segmented copolymer, polyoxyethylene-polyoxypropylene-polyoxyethylene) as a surfactant, and then performing thermal treatment to obtain the anatase type TiO2 nanometer tube, wherein the amount of used glacial acetic acid is 10ml to 50ml; the amount of used TiF4 is 50mg to 150mg; the amount of used F127 is 1g to 5g; the reaction temperature is 160-200 DEG C; the thermal insulation time is 12-48 hours; the thermal treatment temperature is 450-550 DEG C; and the thermal treatment time is 1-3 hours. The solvothermal preparation method of the anatase type TiO2 nanometer tube, disclosed by the invention, is simple in synthesis steps, relatively low in cost, free of use of a strong alkaline solution and applicable to large-scale 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 1 mol/L (NH ₄) H ₂pO ₃solution, after 20V anodic oxidation 15 h, it is main TiO that 1 h 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 (10 mol/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 0.5 g ₂nano particle joins 18 mL 10 mol × L ^-1naOH solution in, proceeded in the water heating kettle of 25 mL after magnetic agitation 30 min and carried out hydro-thermal reaction, at 110 DEG C of reaction 20 h, the white precipitate be obtained by reacting with the HCl of 0.1 mol/L washing several 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, et al, The Design of TiO ₂ Nanostructures (Nanoparticle, Nanotube, and Nanosheet) and Their Photocatalytic Activity[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 0.1 mol × L ^-11 L (NH ₄) ₂tiF ₆in solution, after constant temperature deposits 10 min at 40 DEG C, AAO template is placed in air drying 30 min, finally at 400 DEG C, thermal treatment 4 h 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 1-5g F127(segmented copolymer, polyoxyethylene-poly-oxypropylene polyoxyethylene) pour in glacial acetic acid, stir to clarify;

B. 50-150 mgTiF 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 500 nm 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 20 ml glacial acetic acids to add after in beaker, then weigh 2g F127 and pour in glacial acetic acid, stir to clarify;

B. 100 mgTiF are 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, be incubated 24 h;

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 2 h ₂nanotube.

embodiment two

A. measure 10 ml glacial acetic acids to add after in beaker, then weigh 1g F127 and pour in glacial acetic acid, stir to clarify;

B. 50 mgTiF are 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, be incubated 12 h;

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 3 h ₂nanotube.

embodiment three

A. measure 50 ml glacial acetic acids to add after in beaker, then weigh 5g F127 and pour in glacial acetic acid, stir to clarify;

B. 150 mgTiF are 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, be incubated 48 h;

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 1 h 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 1-5g F127(segmented copolymer, polyoxyethylene-poly-oxypropylene polyoxyethylene) pour in glacial acetic acid, stir to clarify;

B. 50-150 mgTiF 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.