CN104005089A

CN104005089A - Preparation method for self-assembled Bi4Ti3O12 single-crystal nanowire by solvent process

Info

Publication number: CN104005089A
Application number: CN201310060321.6A
Authority: CN
Inventors: 林雪; 车广波; 赵晗
Original assignee: Jilin Normal University
Current assignee: Jilin Normal University
Priority date: 2013-02-27
Filing date: 2013-02-27
Publication date: 2014-08-27
Anticipated expiration: 2033-02-27
Also published as: CN104005089B

Abstract

Belonging to the technical field of nano-material preparation, the invention relates to a preparation method for a self-assembled bismuth titanate single-crystal nanowire by a solvent process. The prepared bismuth titanate single-crystal nanowire has an average diameter of about 50nm, and an X-ray diffractometer, an infrared spectrometer, a Raman spectrometer, a transmission electron microscope and other test approaches are employed to characterize the prepared bismuth titanate single-crystal nanowire. The method has the advantages of simplicity, environmental protection, low cost, rapid reaction and high repeatability, thus having great significance in nano-material synthesis technologies.

Description

Solution method self-assembly Bi 4ti 3o 12the preparation method of monocrystal nanowire

Technical field

The invention belongs to technical field prepared by nano material, particularly a kind of preparation method of solution method self-assembly bismuth titanates monocrystal nanowire.

Background technology

In recent years, Bismuth Titanate-based Ferroelectrics micro/nano material has caused people's concern because combining the special effects of the multiple-effects such as semi-conductive ferroelectric, photochemical catalysis and nano material in preparation and the Application Areas of nano material, 1999, Korea S Park research group reported that on Nature employing pulsed laser deposition (PLD) method prepares La on Pt electrode ³⁺doped bismuth titanate (Bi _3.25la _0.75ti ₃o ₁₂, BLT) ferroelectric membranc, has improved bismuth titanate ferro-electricity membrane fatigue resistance greatly, and intensity of activation is through 10 ¹⁰almost not decay of its ferroelectric properties after inferior fatigue, this great discovery once report, started in the world at once the research boom about bismuth titanates and rare earth doped bismuth titanate ferroelectric material, Bismuth Titanate-based Ferroelectrics material has become in ferroelectric material one of the most potential material, the hot issue that scientific researcher is paid close attention in recent years always, existing many units adopt kinds of experiments method to carry out preparation and the performance study of bismuth titanates material both at home and abroad, the research that simultaneously utilizes first principle to carry out the calculating of bismuth titanates materials theory is reported also a lot, the research of current most bismuth titanates nanometer or micrometer structure aspect is to take the ferroelectric material of rare-earth metal doped ion as main, and mainly concentrate on the researchs such as the preparation of film and ferroelectric properties sign.

Bismuth Titanate-based Ferroelectrics compound comprises Bi ₁₂tiO ₂₀, Bi ₂ti ₂o ₇, Bi ₂₀tiO ₃₂and Bi ₄ti ₃o ₁₂deng.Bi ₄ti ₃o ₁₂conventionally be all ferroelectric material as a kind of excellent property and well known, its crystalline structure is the composite oxides that bismuth layer and perovskite-like layer alternately form, general structure can be expressed as (A _n-1b _no _3n+1) ^2-(Bi ₂o ₂) ²⁺, the former is perovskite-like layer, the latter is bismuth layer, is under the jurisdiction of Aurivillius laminated perovskite family.Wherein A can be Bi, Ba, Sr, Pb, Ca, Ln, K or Na etc., and B is Ti, Ta, W, Cr, Zr, Nb, Mo or Te etc., if A=Bi, B=Ti, n=3, are Bi ₄ti ₃o ₁₂.Calcium titanium ore bed and bismuth layer edge caxle forms separately, and the tetragyre of aspect and oxygen octahedra is perpendicular, and occurs a bismuth layer every n oxygen octahedra, at Bi ₄ti ₃o ₁₂in laminated perovskite structure, perovskite-like layer and (Bi ₂o ₂) ²⁺layer edge cshaft staggered, and between them, formed an internal electric field.Ti-O-Ti bond angle almost reaches 180 ^o, this special structure is conducive to reduce the compound of electron-hole pair, because it may stimulate separated right with hole of electronics and promote light carrier to move to plane of crystal, thereby is conducive to photochemical catalytic oxidation organic pollutant.

At present, possesses special appearance feature and compared with the Bi of bigger serface ₄ti ₃o ₁₂the preparation and property research of micro/nano material has obtained breakthrough, wherein, and low-dimensional nano structure Bi ₄ti ₃o ₁₂because specific surface area is large, structure is special, it is the representative bismuth titanates material that application potential is larger.2011, the people such as Buscagli reported for the first time and have adopted the solid phase method of two kinds of different IPs shell structure reaction template that obtain by colloid chemistry method to prepare Bi ₄ti ₃o ₁₂nanotube one-dimentional structure is low-dimensional Bi ₄ti ₃o ₁₂important basis has been established in the preparation of nanostructure, still, adopts solution self-assembling method to prepare Bi ₄ti ₃o ₁₂monocrystal nanowire, have not been reported.

Summary of the invention

The object of this invention is to provide a kind of solution method self-assembly and prepare Bi ₄ti ₃o ₁₂the method of monocrystal nanowire, the method is simple, repeatable high.

The object of the present invention is achieved like this: the method comprises the following steps: take first in proportion raw material five nitric hydrate bismuth (Bi(NO ₃) ₃5H ₂o), tetra-n-butyl titanate (Ti (OC ₄h ₉) ₄), potassium hydroxide and deionized water, above-mentioned adopted raw material is analytical pure, the mass fraction proportioning of raw material is five nitric hydrate bismuth (Bi(NO ₃) ₃5H ₂o): tetra-n-butyl titanate (Ti (OC ₄h ₉) ₄): potassium hydroxide: deionized water equals 0.6306: 0.3059: 4.48: 10, above-mentioned five nitric hydrate bismuths are dissolved in to deionized water for stirring even, after stirring, continue to stir 30 min and drip again tetra-n-butyl titanate solution, continue again to stir 30 min, then add potassium hydroxide until solution becomes white suspension liquid, then continue to stir 30 min, ultrasonic dispersion 30 min, pack in inner liner polytetrafluoroethylene stainless steel cauldron, packing density is 70 %, in 180 ^oc heats 24 h, and the suspension liquid obtaining after reaction is after ultrasonic dispersion 30 min, and centrifugation, obtains white precipitate, finally white precipitate is respectively washed after 2 times with deionized water and dehydrated alcohol respectively, in vacuum drying oven 100 ^oc is dried, and can obtain Bi ₄ti ₃o ₁₂monocrystal nanowire.

Advantage of the present invention:

1, the technical problem to be solved in the present invention is, discloses a kind of solution method self-assembly and prepares Bi ₄ti ₃o ₁₂the method of monocrystal nanowire; This method is simple, repeatable high.

2, the present invention is at Bi ₄ti ₃o ₁₂in the preparation of monocrystal nanowire, raw material used, is tetra-n-butyl titanate and Bismuth trinitrate, without any need for auxiliary agent and masterplate agent.

3, simple, the environmental protection of method of the present invention, low cost; Repeatable high; Can expand in proportion batch production; Preparation and application aspect at low-dimension nano material hold out broad prospects.

Accompanying drawing explanation

Fig. 1 is prepared Bi ₄ti ₃o ₁₂the XRD figure of monocrystal nanowire.

Fig. 2 is prepared Bi ₄ti ₃o ₁₂the infrared spectrogram of monocrystal nanowire.

Fig. 3 is prepared Bi ₄ti ₃o ₁₂the Raman spectrogram of monocrystal nanowire.

Fig. 4 is prepared Bi ₄ti ₃o ₁₂the transmission electron microscope photo of monocrystal nanowire.

Fig. 5 is prepared Bi ₄ti ₃o ₁₂the local enlarged photograph of monocrystal nanowire.

Fig. 6 is prepared Bi ₄ti ₃o ₁₂the electron diffraction photo of monocrystal nanowire.

Embodiment

Taking 0.6306g five nitric hydrate bismuths, to be dissolved in 10 mL deionized water for stirring even, after stirring, continue to stir 30 min and drip again 0.3059 g tetra-n-butyl titanate solution, continue again to stir 30 min, then add 4.48 g potassium hydroxide until solution becomes white suspension liquid, continue to stir 30 min, ultrasonic dispersion 30 min, pack in inner liner polytetrafluoroethylene stainless steel cauldron again, packing density is 70 %, in 180 ^oc heats 24 h, and the suspension liquid obtaining after reaction is after ultrasonic dispersion 30 min, and centrifugation, obtains white precipitate, white precipitate is respectively washed after 2 times with deionized water and dehydrated alcohol respectively, in vacuum drying oven 100 ^oc is dried, and can obtain Bi ₄ti ₃o ₁₂monocrystal nanowire.

Conclusion:

Fig. 1 is the XRD figure spectrum of prepared sample, and prepared sample is orthohormbic structure Bi as we know from the figure ₄ti ₃o ₁₂(JCPDS card No. 36-1486).Do not observe the diffraction peak of any dephasign, and diffraction peak is sharp-pointed, the crystallization degree of interpret sample is higher.

Fig. 2 is the infrared spectrogram of prepared sample, as we can see from the figure 817 cm ^-1with 601 cm ^-1two strong absorption peaks.These two absorption peaks are Ti-O key stretching vibration peak.

Fig. 3 is the Raman spectrogram of prepared sample, and all diaphragms are all orthohormbic structure Bi ₄ti ₃o ₁₂, 271 cm ^-1can be pointed out as TiO ₆the bending mode of Ti-O key in octahedron, 537 cm ^-1with 851 cm ^-1it is O-Ti-O stretching vibration mould.

Fig. 4 is the transmission electron micrograph of prepared sample, shows that prepared sample is Bi ₄ti ₃o ₁₂nano wire.The diameter of these nano wires is about 50 nm, and length can reach several microns, and its aspect ratio is about 20; These nano wires are without any bifurcated.

The B of Fig. 5 for amplifying _i4ti ₃o ₁₂nano wire transmission electron micrograph, can find out that the nano spherical particle that nano wire inside is about 10 nm by mean sizes forms.

Fig. 6 is Bi ₄ti ₃o ₁₂the selected area electron diffraction figure of nano wire, shows that prepared sample is monocrystal nanowire.

Above-mentioned six figure have proved the sample Bi of preparation ₄ti ₃o ₁₂monocrystal nanowire is laminated perovskite structure, Bi ₄ti ₃o ₁₂monocrystal nanowire is comprised of nano spherical particle, and monocrystal nanowire is grown along [010] crystal orientation.

Claims

1. a solution method self-assembly Bi ₄ti ₃o ₁₂the preparation method of monocrystal nanowire, is characterized in that the method comprises the following steps: take first in proportion raw material five nitric hydrate bismuth (Bi(NO ₃) ₃5H ₂o), tetra-n-butyl titanate (Ti (OC ₄h ₉) ₄), potassium hydroxide and deionized water, above-mentioned adopted raw material is analytical pure, the mass fraction proportioning of raw material is five nitric hydrate bismuth (Bi(NO ₃) ₃5H ₂o): tetra-n-butyl titanate (Ti (OC ₄h ₉) ₄): potassium hydroxide: deionized water equals 0.6306: 0.3059: 4.48: 10, above-mentioned five nitric hydrate bismuths are dissolved in to deionized water for stirring even, after stirring, continue to stir 30 min and drip again tetra-n-butyl titanate solution, continue again to stir 30 min, then add potassium hydroxide until solution becomes white suspension liquid, then continue to stir 30 min, ultrasonic dispersion 30 min, pack in inner liner polytetrafluoroethylene stainless steel cauldron, packing density is 70 %, in 180 ^oc heats 24 h, and the suspension liquid obtaining after reaction is after ultrasonic dispersion 30 min, and centrifugation, obtains white precipitate, finally white precipitate is respectively washed after 2 times with deionized water and dehydrated alcohol respectively, in vacuum drying oven 100 ^oc is dried, and can obtain Bi ₄ti ₃o ₁₂monocrystal nanowire.