CN102974334A - Preparation method of titanium dioxide based composite nanofiber photocatalytic material - Google Patents

Preparation method of titanium dioxide based composite nanofiber photocatalytic material Download PDF

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CN102974334A
CN102974334A CN2012105330475A CN201210533047A CN102974334A CN 102974334 A CN102974334 A CN 102974334A CN 2012105330475 A CN2012105330475 A CN 2012105330475A CN 201210533047 A CN201210533047 A CN 201210533047A CN 102974334 A CN102974334 A CN 102974334A
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based composite
titanium dioxide
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nitrate
dioxide based
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CN102974334B (en
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曹铁平
李跃军
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Abstract

The invention provides a preparation method of a titanium dioxide based composite nanofiber photocatalytic material. The preparation method comprises the following steps of: (1) dissolving a corresponding nitrate in a mixed solution of ethylene glycol and water, adjusting the pH of an obtained mixed solution to 10-12 after the nitrate is completely dissolved, then transferring the obtained mixed solution to a polytetrafluoroethylene reaction kettle, adding TiO2 nanofibers prepared by an electrostatic spinning method to the mixed solution, placing the reaction kettle in a drying oven, adjusting a reaction temperature to 120-180 DEG C, and controlling the heating time to 12-24h; and (2) naturally cooling a reaction system to room temperature, washing an obtained sample for several times by respectively using absolute ethyl alcohol and distilled water, and drying for 10-12h in the drying oven at the temperature of 60 DEG C to obtain the titanium dioxide based composite nanofiber photocatalytic material. The preparation method is simple in a synthesis technology and can be used for preparing the titanium dioxide based composite nanofiber photocatalytic material with the controlled shape, excellent performance and heterostructure; and the catalytic material has the advantages of high photocatalytic activity, easiness in separation, recovery and recycling and very wide market prospect.

Description

The preparation method of titanium dioxide based composite nano fiber catalysis material
Technical field
The present invention relates to a kind of preparation method of titanium dioxide based composite nano fiber catalysis material.
Background technology
One piece of paper that the research origin of photochemical catalytic oxidation is delivered at " Nature " magazine in Fujishima and the Honda of Japan in 1972, it indicates that photocatalysis research has begun new epoch.Carey etc. use TiO under UV-irradiation 2Success degraded extremely toxic substance Polychlorinated biphenyls, thus the application of conductor photocatalysis in environmental pollution treatment opened up.In the middle of numerous conductor photocatalysis materials, TiO 2Because the advantages such as its photocatalytic activity is high, ultraviolet-shielding type is strong, thermal conductance good, good dispersion and inexpensive, nontoxic, non-secondary pollution become the most valued a kind of photocatalytic semiconductor material.Utilize electrostatic spinning technique, be that driving force prepares organic high polymer nanometer fiber by high-pressure electrostatic at first, then prepare the Nano titanium dioxide fiber through the method for high-temperature roasting, this fiber have nanometer diameter, nanometer level microporous, great specific area, etc. characteristic and make it show good application prospect in fields such as air cleaning, sewage system reason and sterilizings.
Yet, TiO in actual applications 2Also there are two inherent shortcomings, the one, greater band gap (anatase Eg=3.2eV) can only be by the ultraviolet excitation of wavelength less than λ＜387.5nm, and ultraviolet light only accounts in solar spectrum about 5%, the sunshine utilization rate is low; The 2nd, light induced electron and hole are very easy to compound, cause its photo-quantum efficiency poor, and this just hinders its industrial applications process.At present, to TiO 2Carry out modification, widen it to the response range of solar spectrum, improve the utilization rate of sunshine, the right Simple fast in establishment light induced electron and hole is compound, improve the purpose that its photocatalytic activity reaches suitability for industrialized production, become study hotspot and the key technology in this field.
Composite semiconductor (titanium dioxide, titanate) claims again hetero-junctions, utilize two kinds of semi-conductive conduction bands, valence-band level difference, form potential barrier and energy valley at interface, change the transition process of photo-generated carrier, reduced the recombination rate in light induced electron-hole, the separation of charge effect of raising system, expansion TiO 2Spectral response range, thus promote the photochemical catalyst electron-hole to separate, improve the photochemical catalyst catalytic efficiency.
Summary of the invention
Owing to be similar to size shape and the TiO of this multicomponent oxidate nano crystal particle of titanate 2Nanofiber is not easy to coincide, therefore the object of the present invention is to provide a kind of preparation method of titanium dioxide based composite nano fiber catalysis material, by selecting suitable material and best reaction condition to make both better compound, make the titanate crystals growth in situ at TiO 2The nanofiber surface is effectively combined closely the two, thereby is prepared desirable titanium dioxide base composite nano catalysis material.
For achieving the above object, the present invention is by the following technical solutions:
A kind of preparation method of titanium dioxide based composite nano fiber catalysis material may further comprise the steps:
(1) corresponding nitrate is dissolved in the mixed solution of ethylene glycol and water and obtains nitrate solution, the pH that regulates this nitrate solution is 10～12, then transfers them in the polytetrafluoroethylene (PTFE) reactor, to wherein adding freshly prepd TiO 2Nanofiber places that the conditioned reaction temperature is 120～180 ℃ in the baking oven, and control heat time heating time is 12～24h;
(2) make reaction system naturally cool to room temperature, the gained sample is cleaned several times with absolute ethyl alcohol and distilled water respectively, 60 ℃ of drying 10～12h obtain TiO in baking oven 2The based composite nano fiber catalysis material.
In said method, described nitrate is calcium nitrate, barium nitrate or plumbi nitras.The volume ratio of ethylene glycol and water is 1: 4～1: 5 in the mixed solution of described ethylene glycol and water.The concentration of nitrate is 5～50mmol/L in the described nitrate solution.
In described step (1), nitrate and TiO 2The ratio of the amount of substance between the nanofiber is 1: 1.25; Described TiO 2Nanofiber adopts electrostatic spinning technique to make.
In said method, TiO 2Nanofiber carries out chemical reaction with reactant in the solution and generates corresponding titanate under this particular surroundings of HTHP, along with the titanate concentration of constantly carrying out generating of reacting increases, when reaching capacity, concentration begins crystallization, owing to adopt the TiO of electrostatic spinning technique preparation 2Nanofiber has three-dimensional open structure, high porosity and very large surface-active, and the crystal of therefore separating out is just with TiO 2Nanofiber is the matrix growth in situ, and the final nano particle with different-shape that forms is constructed at TiO 2The nanofiber surface makes titanium dioxide based composite nano fiber catalysis material.
In said method, can effectively control by changing various response parameters (such as reaction temperature, concentration and time etc.) pattern, particle size of titanate particle and at TiO 2The coverage density of fiber surface.
The invention has the advantages that:
The present invention is is fully understanding and grasping TiO according to the hydro-thermal reaction characteristics 2On the hydrothermal reaction process of nanofiber and the basis of reaction mechanism, effectively control the pattern, particle size of titanate nanoparticle by adjusting the factors such as reaction temperature, concentration and time and at TiO 2The coverage density of fiber surface, thus obtain that structure is controlled, excellent performance, have the titanium dioxide based composite nano fiber catalysis material of heterojunction structure.
Synthesis technique of the present invention is simple, utilizes organic matter in the sunshine degradation of sewage, and photocatalytic activity is high, easily separated recovery and recycling, energy-conservation, non-secondary pollution, applied range, environmental protection, and market prospects are boundless.
Description of drawings
Fig. 1 is the embodiment of the invention 1,2 employed TiO 2The scanning electron microscope (SEM) photograph of nanofiber.
Fig. 2 is the embodiment of the invention 1 prepared CaTiO 3/ TiO 2The scanning electron microscope (SEM) photograph of composite nano fiber.
Fig. 3 is the embodiment of the invention 2 prepared BaTiO 3/ TiO 2The scanning electron microscope (SEM) photograph of composite nano fiber.
The specific embodiment
The present invention will be further described by the following examples.
Material preparation and test instrument and medicine
Polyvinylpyrrolidone (PVP, M s=1300000, chemical pure, Beijing Yili Fine Chemicals Co., Ltd.); Tetrabutyl titanate (analyze pure, Shanghai elder brother row Chemical Industry Science Co., Ltd); Barium nitrate, calcium nitrate (analyze pure, Beijing Yili Fine Chemicals Co., Ltd.); Ethylene glycol, absolute ethyl alcohol, glacial acetic acid (it is pure to be analysis, the Beijing Chemical Plant).
The phase of material characterizes and adopts Rigaku D/max 2500V PC X-ray diffraction (XRD Japan Ricoh), and x-ray source is Cu K α line, and sweep speed is 2min -1, wavelength X=0.15405nm, accelerating potential are 40kV, electric current is 40mA, adopts the display detector, and 20 °～60 ° of sweep limits, going on foot wide is 0.02 °.The pattern of material characterizes on Hitachi S-570 (15kV) field emission scanning electron microscope (FESEM, HIT), and has connected X-ray diffraction (EDS), and accelerating potential is 15kV.The structure of material and pattern are by high resolution transmission electron microscopy (HRTEM, JEOL JEM-2010, accelerating potential 100kV).Adopt the absorbance of Cary 500 ultraviolet-visible-near-infrared spectrum instrument (UV-VIS-NIR) the mensuration RB solution of U.S. Varian company.
TiO 2The preparation of nanofiber
Get 1.0gPVP and be dissolved in the 10mL absolute ethyl alcohol, magnetic agitation 4h makes solution A; With 1.5mL tetrabutyl titanate (Ti (OBu) 4) under agitation slowly be added drop-wise in the mixed solution of 3mL absolute ethyl alcohol and 3mL glacial acetic acid, continue to stir 30min, make solution B; Under the room temperature solution B slowly is added drop-wise in the solution A, strong stirring 2h makes PVP/Ti (OBu) 4Colloidal sol.
Adopt commercially available electrostatic spinning apparatus to prepare TiO 2Nanofiber, this electrostatic spinning apparatus mainly contain three parts and form: electrostatic high-pressure power supply, fluid Supplying apparatus, fiber collecting device.With an amount of PVP/Ti (OBu) 4In the colloidal sol filling liquid feedway (syringe), metal electrode probes in the front end capillary.Adjusting syringe angle of inclination is about and horizontal plane is at 45 °.The distance of capillary tip and dash receiver is 15cm, applies the voltage of 12kV.Time of reception is 5h, obtains one deck fibrofelt.Taking-up is tiled in the Noah's ark behind the vacuum drying 24h, places Muffle furnace to heat, and programming rate is 4 ℃/min.When temperature rises to 500 ℃, constant temperature 10h makes TiO 2Nanofiber.
Be illustrated in figure 1 as the TiO of new system 2The scanning electron microscope (SEM) photograph of nanofiber, as seen from the figure, fiber surface is smooth, does not have other species to adhere to, and its diameter is about about 200～300nm.
Embodiment 1
CaTiO 3/ TiO 2The preparation of composite nano fiber: take by weighing 0.023g Ca (NO 3) 2.4H 2O is dissolved in 20mL ethylene glycol and water (V Ethylene glycol: V Water=1: in the mixed solution 4), treat that it dissolves fully, the acid-base value that drips KOH solution conditioned reaction liquid to pH be 11.Transfer in the 25mL polytetrafluoroethylene (PTFE) reactor, add again 0.01gTiO 2Fiber, sealing are placed on 180 ℃ of heating 24h in the baking oven.Naturally cool to room temperature, clean several times with distilled water and absolute ethyl alcohol, place 60 ℃ of dry 10h of baking oven, make CaTiO 3/ TiO 2The composite nano fiber catalysis material.
Be illustrated in figure 2 as the CaTiO that present embodiment makes 3/ TiO 2The scanning electron microscope (SEM) photograph of composite nano fiber catalysis material, high-visible sample still keeps original fibre morphology from figure, but the surface is no longer smooth, and many CaTiO are arranged 3Nanocube is grown in TiO equably 2Fiber surface does not have agglomeration.
Embodiment 2
BaTiO 3/ TiO 2The preparation of composite nano fiber: take by weighing 0.026g Ba (NO 3) 2Be dissolved in 20mL ethylene glycol and water (V Ethylene glycol: V Water=1: in the mixed solution 5), treat that it dissolves fully, the acid-base value that drips sodium hydroxide solution conditioned reaction liquid to pH be 11.Transfer in the 25mL polytetrafluoroethylene (PTFE) reactor, add again 0.01gTiO 2Fiber, sealing are placed on 180 ℃ of heating 12h in the baking oven.Naturally cool to room temperature, clean several times with absolute ethyl alcohol and distilled water respectively, place 60 ℃ of dry 10h of baking oven, make BaTiO 3/ TiO 2The composite nano fiber catalysis material.
Be illustrated in figure 3 as the BaTiO that present embodiment makes 3/ TiO 2The scanning electron microscope (SEM) photograph of composite nano fiber catalysis material, high-visible sample also still keeps original fibre morphology from figure, but the surface is no longer smooth, and many BaTiO are arranged 3Nanosphere is grown in TiO equably 2Fiber surface does not have agglomeration, and fibre diameter is compared with fibrillation slightly and increased.
The visible light catalytic performance of embodiment 1,2 gained samples has been investigated in take the decolored degradation of rhodamine B as pattern reaction.The result shows: CaTiO 3, BaTiO 3Be grown in equably TiO etc. titanate nanoparticle 2The nanofiber surface has formed the titanium dioxide based composite nano fiber catalysis material with heterojunction structure.The original position of titanate is compounded with and is beneficial to TiO 2Strengthened the quantum efficiency of system separating of light induced electron and hole, Effective Raise the sunshine utilization rate, its spectral response range is by TiO 2The ultraviolet region of nanofiber (387.5nm) is widened to visible region (450.6nm and 512.3nm).Behind the illumination 8h, the percent of decolourization of RB reaches 87.8%.And under the same terms, pure TiO 2The percent of decolourization of nanofiber only has 14.5%, shows that titanate nanoparticle is at TiO 2The growth in situ Effective Raise on nanofiber surface TiO 2Visible light photocatalysis active at nanofiber.

Claims (6)

1. the preparation method of a titanium dioxide based composite nano fiber catalysis material is characterized in that, may further comprise the steps:
(1) corresponding nitrate is dissolved in the mixed solution of ethylene glycol and water and obtains nitrate solution, the pH that regulates this nitrate solution is 10～12, then transfers them in the polytetrafluoroethylene (PTFE) reactor, to wherein adding freshly prepd TiO 2Nanofiber places that the conditioned reaction temperature is 120～180 ℃ in the baking oven, and control heat time heating time is 12～24h;
(2) make reaction system naturally cool to room temperature, the gained sample is cleaned several times with absolute ethyl alcohol and distilled water respectively, in baking oven, in 60 ℃ of drying 10～12h, obtain TiO 2The based composite nano fiber catalysis material.
2. the preparation method of titanium dioxide based composite nano fiber catalysis material according to claim 1 is characterized in that, described nitrate is calcium nitrate, barium nitrate or plumbi nitras.
3. the preparation method of titanium dioxide based composite nano fiber catalysis material according to claim 1 is characterized in that, the volume ratio of ethylene glycol and water is 1: 4～1: 5 in the mixed liquor of described ethylene glycol and water.
4. the preparation method of titanium dioxide based composite nano fiber catalysis material according to claim 1 is characterized in that, the concentration of nitrate is 5～50mmol/L in the described nitrate solution.
5. the preparation method of titanium dioxide based composite nano fiber catalysis material according to claim 1 is characterized in that, in described step (1), and nitrate and TiO 2The ratio of the amount of substance between the nanofiber is 1: 1.25.
6. the preparation method of titanium dioxide based composite nano fiber catalysis material according to claim 1 is characterized in that described TiO 2Nanofiber adopts electrostatic spinning technique to make.
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Cited By (2)

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Publication number Priority date Publication date Assignee Title
CN103276475A (en) * 2013-05-30 2013-09-04 常熟理工学院 Preparation method of heteropoly acid/metal oxide composite nano fiber
CN110540430A (en) * 2019-08-12 2019-12-06 西安理工大学 Preparation method of piezoelectric photocatalytic composite fiber with multi-stage structure

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103276475A (en) * 2013-05-30 2013-09-04 常熟理工学院 Preparation method of heteropoly acid/metal oxide composite nano fiber
CN103276475B (en) * 2013-05-30 2015-04-15 常熟理工学院 Preparation method of heteropoly acid/metal oxide composite nano fiber
CN110540430A (en) * 2019-08-12 2019-12-06 西安理工大学 Preparation method of piezoelectric photocatalytic composite fiber with multi-stage structure
CN110540430B (en) * 2019-08-12 2021-10-22 西安理工大学 Preparation method of piezoelectric photocatalytic composite fiber with multi-stage structure

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