CN103240068B - Preparation method of self-doped titanium dioxide nanorod - Google Patents
Preparation method of self-doped titanium dioxide nanorod Download PDFInfo
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Abstract
The invention provides a preparation method of a self-doped titanium dioxide nanorod. The method comprises the following steps of: adding butyl titanate [Ti(OC4H9)4] into liquor of hydrazine (N2H4.H2O) and ethylene glycol (C2H6O2); powerfully stirring; then, transferring to a reaction kettle lined with polyvinyl fluoride; maintaining the constant temperature at 200 DEG C for 12-24 hours; naturally cooling to room temperature; and filtering, washing and drying to obtain the self-doped titanium dioxide nanorod provided by the invention. According to the method provided by the invention, self-doped titanium dioxide is directly reduced in a liquid phase without thermal reduction treatment. The preparation method is simple in process, and the self-doped TiO2 nanorod is controllable in size and uniform in dimension, and the average length is 50-80nm and the average diameter is 8-15nm. The self-doped titanium dioxide nanorod prepared by the method provided by the invention is expected to be widely applied to the fields of hydrogen generation by photolysis of water, degradation of organic pollutants and the like.
Description
Technical field
The present invention relates to a kind of preparation method of titanium dioxide nano-rod, be specifically related to a kind of preparation method of auto-dope titanium dioxide nano-rod.
Background technology
Environmental pollution is a great problem of puzzlement current world economy development.A large amount of use fossil fuel not only causes huge pollution to global environment and ecology, and these energy are non-renewable resources, and the storage content in the whole world estimates that the middle of this century is about to exhaustion.Therefore, problem of environmental pollution how is solved extremely urgent.Since Honda and Fujishima in 1972 etc. find TiO
2since Single Crystalline Electrodes has certain redox property under the effect of light, scientists is solve environmental pollution this difficult problem to propose an energy-efficient solution: utilize sunshine to carry out decomposing organic pollutant.
Traditional semiconductor light-catalyst mainly inorganic compound, comprise metal oxide, sulfide, nitride, phosphide and compound thereof etc., most is representational is TiO
2.TiO
2water insoluble, resistance to corrosion strong, cheap and conveniently process, the advantage such as biological function, photochemical properties are stable, environmentally safe, become a kind of desirable photochemical catalyst.But TiO
2band gap be 3.2 eV, only have wavelength just can excite the transition of valence-band electrons lower than the ultraviolet light of 380 below nm, and solar spectrum medium ultraviolet light is less than 5%, and the visible ray that wavelength is 400-750 nm accounts for about 45%, this fundamentally constrains TiO
2the practical application of photochemical catalyst.At present, researcher widens TiO by methods such as doping, semiconductors coupling, dye sensitization, noble-metal-supported and conjugated polymers compounds
2light absorption band edge, improve photocatalytic activity.Doping is to TiO
2a kind of effective method of modification, but due in most cases, the ion of external doping can serve as the complex centre in light induced electron and hole, and the impurity level that external doping is formed is normally uneven discontinuous, thus causes the migration in light induced electron and hole to have difficulties.In addition, some thermal instabilitys of simultaneously causing of doped chemical.
Except external ion doping, auto-dope be also a kind of regulate and control band structure and improve the effective means of quantum efficiency.Auto-dope TiO
2be a kind of structure uniqueness and be rich in potentiality visible-light photocatalyst, but up to now, auto-dope TiO
2investigation and application report seldom, main cause is due to auto-dope TiO
2preparation method complicated, condition is harsh, expensive equipment etc.
In the preparation of titanium dioxide nano-rod, current preparation method mainly template, template needs to remove template with chemical method after preparation completes, and operation is comparatively complicated.Sol-gel process, as patent CN101025556 discloses a kind of method adopting electric field heat treatment to prepare highlight catalytic active nano titania powder, although sol-gel process is a kind of preparation method using more nano material at present, the titanium dioxide that its technique directly obtains mostly is unformed phase.And for example patent CN 1986907A discloses a kind of reaction mechanism using for reference sol-gel process template, prepares a kind of method of titanium dioxide nano thread, and the method needs high reaction temperature, and reaction time consumption.Hydrothermal synthesis method, as, CN 1669636A discloses a kind of method that hydrothermal synthesis method prepares titanic oxide material, and the 1-dimention nano titanic oxide material length that the method obtains is uneven, obtained tube diameters is 20-50 nanometer, and length is several microns and arrives hundreds of micron.Patent CN 101468812B is for the deficiency of hydrothermal synthesis method, disclose a kind of method by titanium dioxide nano-rod being prepared by rear for the heating of titania nanoparticles, alkali metal hydroxide and ORGANIC SOLVENT MIXTURES and surfactant fluid, obtained titanium dioxide nano-rod length is homogeneous, and reaction can be carried out at ambient pressure.
Summary of the invention
The object of the present invention is to provide a kind of preparation method of auto-dope titanium dioxide nano-rod, this preparation method without in the past first prepare TiO
2the complicated technology using reducibility gas to carry out reduction treatment again in tube furnace to prepare auto-dope titanium dioxide, and solve the pattern of high-temperature process to product and the problem of stability influence, there is the advantage that preparation technology is simple, with low cost, quick, energy-conservation and efficiency is high, adopt the auto-dope TiO that this preparation method prepares
2nanometer rods size is controlled, size is even, average length at 50-80 nm, average diameter at 8-15 nm, this auto-dope TiO
2nanometer rods product is expected to obtain in the field such as photolysis water hydrogen, degradable organic pollutant apply widely.
The preparation method of auto-dope titanium dioxide nano-rod of the present invention, comprises the steps:
(1) butyl titanate is joined in the mixed solution of hydrazine and ethylene glycol, wherein butyl titanate: hydrazine: the volume ratio of ethylene glycol is 1:1 ~ 3:13.5 ~ 15.5, strong stirring 15 ~ 60 min, obtain mixed liquor;
(2) mixed liquor that step (1) obtains is transferred in the hydrothermal reaction kettle of liner four polyvinyl fluoride;
(3) hydrothermal reaction kettle of liner four polyvinyl fluoride is placed in drying box, keeps constant temperature 200 DEG C, reaction 12 ~ 24 h, then naturally cool to room temperature;
(4) step (3) products therefrom is filtered, precipitate each three times with distilled water, absolute ethanol washing, then at 60 ~ 80 DEG C, dry 12 ~ 24 h, obtained auto-dope titanium dioxide nano-rod.
In described preparation method, optimum condition is: butyl titanate in mixed liquor: hydrazine: the weight ratio of ethylene glycol is 1:1.5:15, under solvent heat condition, and drying box constant temperature 200 DEG C, reaction time 24 h.
Keep constant temperature 200 DEG C in described step (3), reaction 12 ~ 24 h refer to: under solvent heat condition, drying box constant temperature is at 200 DEG C, and constant temperature time is 12 ~ 24 h.
In described step (3), thermostat temperature keeps stable, and temperature fluctuation range is ± 0.1 DEG C.
Described butyl titanate is pure for analyzing, and purity is 99.9%, and hydrazine is N
2h
4h
2o, purity is 80%.
The auto-dope titanium dioxide nano-rod adopting the present invention to prepare is applied in visible ray catalyzes degraded organic contamination reaction, such as at normal temperatures, reaction time is 2.5h, and result shows that auto-dope titanium dioxide nano-rod prepared by the present invention has higher catalytic activity.
D8 ADVANCE type X-ray powder diffractometer (XRD) that adopts German Bruker company to produce to the auto-dope titanium dioxide nano-rod adopting the preparation method of auto-dope titanium dioxide nano-rod of the present invention to obtain (
λ cu =0.15418 nm) carry out Crystalline form analysis (as Fig. 1), result shows: products therefrom is anatase titania; Adopt LEO1530VP type field emission scanning electron microscope (SEM) to carry out morphology analysis (as Fig. 2), result shows: auto-dope titanium dioxide is bar-shaped, and particle is less and even, is about 50-80 nm, wide about 10-15 nm; Adopt the photoelectricity power spectrum of Britain VG ESM-LAB to carry out XPS analysis (as Fig. 3) to obtained material, result shows to there is Ti in product simultaneously
3+and Ti
4+, illustrate to there is auto-doping phenomenon.
The auto-dope titanium dioxide nano-rod adopting the preparation method of auto-dope titanium dioxide nano-rod of the present invention to prepare and pure titinium dioxide nanometer rods, nitrogen-doped titanium dioxide (N-P25) have been carried out to the expression activitiy (as Fig. 4) of photo-catalytic degradation of methyl-orange under visible ray effect, result shows that the auto-dope titanium dioxide nano-rod prepared has most high activity.This photochemical catalyst can in the extensive use such as photolysis water hydrogen, degradable organic pollutant.
The present invention compared with prior art has following advantage and effect:
(1) its technology preparation condition of preparation method of the present invention is gentleer, and equipment is simple, without in the past first prepare TiO
2, then the complicated technology using reducibility gas to carry out reduction treatment in tube furnace to prepare auto-dope titanium dioxide, thus avoid high-temperature process to the pattern of product and stability influence;
(2) direct-reduction hydrolysis obtains Detitanium-ore-type auto-dope titanium dioxide nano-rod under hydrothermal conditions, prepared titanium dioxide nano-rod has less and even, visible light photocatalysis active the is high advantage of particle, particularly without the need to high temperature crystallization, directly obtain anatase titanium dioxide;
(3), compared with the effect that the auto-dope titanium dioxide nano-rod prepared of the present invention and pure titinium dioxide nanometer rods, nitrogen-doped titanium dioxide (N-P25) have carried out photo-catalytic degradation of methyl-orange under visible ray effect, there is more high catalytic activity.
Accompanying drawing explanation
Fig. 1 is auto-dope titanium dioxide nano-rod X-ray powder diffraction (XRD) figure that the present invention obtains.
Fig. 2 is auto-dope titanium dioxide nano-rod SEM (SEM) figure that the present invention obtains.
Fig. 3 is auto-dope titanium dioxide nano-rod photoelectron spectroscopy (XPS) collection of illustrative plates that the present invention obtains.
The effectiveness comparison figure of photo-catalytic degradation of methyl-orange under Fig. 4 to be auto-dope titanium dioxide nano-rod (c) that obtains of the present invention with pure titinium dioxide nanometer rods (a), nitrogen-doped titanium dioxide (N-P25) (b) carried out visible ray effect.
Detailed description of the invention
Explain the present invention further below in conjunction with embodiment, but embodiment does not limit in any form to the present invention.
Embodiment 1: add 4 ml hydrazine (N in the beaker of 250 ml
2h
4h
2o, 80%) and 62 ml ethylene glycol (C
2h
6o
2), magnetic agitation 10 min, then slowly adds 4 ml butyl titanate (Ti (OC
4h
9)
4), i.e. butyl titanate: hydrazine: the volume ratio of ethylene glycol is 1:1:15.5, strong stirring 30 min, then transfers in 100ml liner four polyvinyl fluoride hydrothermal reaction kettle, puts in 200 DEG C of thermostatic drying chambers, under solvent heat condition, keeps reaction 24 h.After reaction terminates, naturally cool to room temperature, respectively wash three times with distilled water and absolute ethyl alcohol, obtained after product being placed in 70 DEG C of drying box vacuum drying 24 h.The titanium dioxide nano-rod adopting this step to prepare is about 70-80 nm, wide about 10-15 nm.
Embodiment 2: add 6 ml hydrazine (N in the beaker of 250 ml
2h
4h
2o, 80%) and 60 ml ethylene glycol (C
2h
6o
2), magnetic agitation 10 min, then slowly adds 4 ml butyl titanate (Ti (OC
4h
9)
4), i.e. butyl titanate: hydrazine: the volume ratio of ethylene glycol is 1:1.5:15, strong stirring 60 min, then transfers in 100 ml liner four polyvinyl fluoride hydrothermal reaction kettles, puts in 200 DEG C of thermostatic drying chambers, under solvent heat condition, keeps reaction 24 h.After reaction terminates, naturally cool to room temperature, respectively wash three times with distilled water and absolute ethyl alcohol, product is placed in 80 DEG C of drying box vacuum drying 12 h.The titanium dioxide nano-rod adopting this step to prepare is about 70-80 nm, wide about 10-15 nm.
Embodiment 3: add 12 ml hydrazine (N in the beaker of 250 ml
2h
4h
2o, 80%) and 54 ml ethylene glycol (C
2h
6o
2), magnetic agitation 10 min, then slowly adds 4 ml butyl titanate (Ti (OC
4h
9)
4), i.e. butyl titanate: hydrazine: the volume ratio of ethylene glycol is 1:3:13.5, strong stirring 15min, then transfers in 100 ml liner four polyvinyl fluoride hydrothermal reaction kettles, puts in 200 DEG C of thermostatic drying chambers, under solvent heat condition, keeps reaction 24 h.After reaction terminates, naturally cool to room temperature, respectively wash three times with distilled water and absolute ethyl alcohol, product is placed in 60 DEG C of drying box vacuum drying 18 h.The titanium dioxide nano-rod adopting this step to prepare is about 60-80 nm, wide about 10-15 nm.
Embodiment 4: add 6 ml hydrazine (N in the beaker of 250 ml
2h
4h
2o, 80%) and 60 ml ethylene glycol (C
2h
6o
2), magnetic agitation 10 min, then slowly adds 4 ml butyl titanate (Ti (OC
4h
9)
4), i.e. butyl titanate: hydrazine: the volume ratio of ethylene glycol is 1:1.5:15, strong stirring 30 min, then transfers in 100 ml liner four polyvinyl fluoride hydrothermal reaction kettles, puts in 200 DEG C of thermostatic drying chambers, under solvent heat condition, keeps reaction 18 h.After reaction terminates, naturally cool to room temperature, respectively wash three times with distilled water and absolute ethyl alcohol, product is placed in 70 DEG C of drying box vacuum drying 24 h.The titanium dioxide nano-rod adopting this step to prepare is about 50-80 nm, wide about 8-12 nm.
Embodiment 5: add 6 ml hydrazine (N in the beaker of 250 ml
2h
4h
2o, 80%) and 60 ml ethylene glycol (C
2h
6o
2), magnetic agitation 10 min, then slowly adds 4 ml butyl titanate (Ti (OC
4h
9)
4), i.e. butyl titanate: hydrazine: the volume ratio of ethylene glycol is 1:1.5:15, strong stirring 40 min, then transfers in 100 ml liner four polyvinyl fluoride hydrothermal reaction kettles, puts in 200 DEG C of thermostatic drying chambers, under solvent heat condition, keeps reaction 12 h.After reaction terminates, naturally cool to room temperature, respectively wash three times with distilled water and absolute ethyl alcohol, product is placed in 75 DEG C of drying box vacuum drying 20 h.The titanium dioxide nano-rod adopting this step to prepare is about 50-80 nm, wide about 8-15 nm.
Claims (2)
1. a preparation method for auto-dope titanium dioxide nano-rod, is characterized in that: comprise the steps:
(1) butyl titanate is joined in the mixed solution of hydrazine and ethylene glycol, wherein butyl titanate: hydrazine: the volume ratio of ethylene glycol is 1:1 ~ 3:13.5 ~ 15.5, strong stirring 15 ~ 60 min, obtain mixed liquor;
(2) mixed liquor that step (1) obtains is transferred in the hydrothermal reaction kettle of inner liner polytetrafluoroethylene;
(3) hydrothermal reaction kettle of inner liner polytetrafluoroethylene is placed in drying box, keeps constant temperature 200 DEG C, reaction 12 ~ 24 h, then naturally cool to room temperature;
(4) step (3) products therefrom is filtered, precipitate each three times with distilled water, absolute ethanol washing, then at 60 ~ 80 DEG C, dry 12 ~ 24 h, obtained auto-dope titanium dioxide nano-rod;
Keep constant temperature 200 DEG C described in step (3), reaction 12 ~ 24 h refer to: under solvent heat condition, drying box constant temperature is at 200 DEG C, and constant temperature time is 12 ~ 24 h;
Thermostat temperature described in step (3) keeps stable, and temperature fluctuation range is ± 0.1 DEG C.
2. the preparation method of auto-dope titanium dioxide nano-rod according to claim 1, is characterized in that: described butyl titanate is pure for analyzing, and purity is 99.9%, and hydrazine is N
2h
4h
2o, purity is 80%.
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| CN107824181A (en) * | 2017-10-26 | 2018-03-23 | 上海应用技术大学 | A kind of preparation method of visible-light photocatalyst |
| CN109277094A (en) * | 2018-10-18 | 2019-01-29 | 浙江工商大学 | A kind of method of modifying of visible light responsive photocatalyst and its application in artificial seawater system |
| CN110947410B (en) * | 2019-12-11 | 2023-10-24 | 信阳师范学院 | Nitrogen-doped TiO 2 Mild preparation method of micrometer beam |
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Non-Patent Citations (2)
| Title |
|---|
| Self-doped Ti3+-enhanced TiO2 nanoparticles with a high-performance photocatalysis;Mingyang Xing et al;《Journal of Catalysis》;20121121;第297卷;第237页第2.1节 * |
| 氮掺杂TiO2异质结构的制备及其光催化性能研究;段秀全;《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》;20111015;第20页第2.3节，第22页第2.5.5节和第23页图2.1 * |
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