CN101643938A

CN101643938A - Method for preparing submicron grade square pipe-shaped Sb2Se3

Info

Publication number: CN101643938A
Application number: CN200910034771A
Authority: CN
Inventors: 姬广斌; 施毅; 潘力嘉; 郑有炓
Original assignee: Nanjing University
Current assignee: Nanjing University
Priority date: 2009-09-08
Filing date: 2009-09-08
Publication date: 2010-02-10
Anticipated expiration: 2029-09-08
Also published as: CN101643938B

Abstract

The invention relates to a method for preparing submicron grade square pipe-shaped Sb2Se3. The method comprises the following steps: adding SbCl3 and Na2SeO3 with the substance amount ratio of 2:3 atroom temperature into glycerin liquid, magnetically stirring for 0.5-2 hours and placing the mixture into a microwave reaction vessel to be heated for 8-10 min; cooling and then alternately washing the product by alcohol and water repeatedly; drying in a vacuum drying oven and then acquiring a submicron grade Sb2Se3 square pipe. The acquired Sb2Se3 is the submicron grade square pipe, has the pipelength of 10-20 microns, the pipe opening width of 0.5-1 micron and the pipe wall thickness of 100-200 nm and grows along the (001) direction. The method for preparing the Sb2Se3 submicron grade square pipe is simple and convenient, has simple used equipment and short time consumption, can realize large-scale preparation in short time and is convenient for industrialized production.

Description

A kind of submicron grade square pipe-shaped Sb 2Se 3The preparation method

Technical field

The invention belongs to the synthetic field of inorganic nano material, be specifically related to submicron order Sb2Se3 semiconductor material of a kind of square pipe-shaped pattern and preparation method thereof.

Background technology

Sb ₂Se ₃Be a kind of direct band-gap semicondictor material, have laminate structure, belong to rhombic system.Because it has excellent photoelectric properties, high thermoelectric transformation efficiency, and transition effects are subjected to increasing attention, and are widely used in light selectivity and decorative coating, thermoelectric refrigeration and photochemistry device, and field such as initial storage transfer equipment.Traditionally, Sb ₂Se ₃Be under hot conditions, to react synthetic by simple substance Sb and Se.Now, many wet chemical methods are applied to synthetic Sb ₂Se ₃Nanocrystalline, as methods such as hydro-thermal, solvent thermal.Many one dimension Sb ₂Se ₃Nanocrystalline nano wire, nanometer rod, nano belt, the micron tube of comprising has been successfully synthesized.Because have outstanding mechanical property and unique electron motion characteristic, nano tubular structure is subjected to scientific circles and pays close attention to widely.Other one-dimentional structures are because nanotube has unique cavernous structure, more difficult synthetic relatively.Former study shows, the material that can synthesize tubular structure need have and is similar to the same laminate structure of graphite.Though Sb ₂Se ₃Also have laminate structure, but few people successfully synthesize tubulose Sb so far ₂Se ₃2002, people such as the Xie Yi Sb that reported for work ₂Se ₃Microtubule.They adopt solvent-thermal method, with SbCl ₃With the Se powder be raw material, in ethanolic soln, 180 ℃ of down reactions 7 days successfully synthesize Sb ₂Se ₃Tubular structure (Xiuwen Zheng, Yi Xie, Liying Zhu, Xuchuan Jiang, Yunbo Jia, Wenhai Song, and Yuping Sun.Inorg.Chem.2002,41 (3), 455-461.).The synthetic Sb of institute ₂Se ₃Pipe is a micron order four directions pipe, pipe range 5-10mm, the wide 10-20 μ of mouth of pipe m, thick 5-10 μ m.Because institute's synthetic micron order four directions pipe is oversize, can not present the excellent properties of nanotube, its application is subjected to certain limitation.Simultaneously because the reaction times is long, output is low excessively, has also influenced its industrialization greatly.The present invention adopts microwave-assisted poly-hydroxy method, with SbCl ₃And Na ₂SeO ₃Being raw material, is solvent and reductive agent with the glycerol, and microwave heating 8-10min successfully synthesizes submicron grade square tubular construction Sb ₂Se ₃The synthetic Sb of institute ₂Se ₃Pipe, pipe range 10-20 μ m, the wide 0.5-1 μ of mouth of pipe m, thickness of pipe 100-200nm is along the growth of (001) direction.Size is near nano level, much smaller than bibliographical information.This method is simple, consuming time extremely short, is convenient to suitability for industrialized production.

Summary of the invention

Technical problem to be solved by this invention provides a kind of submicron grade square pipe-shaped Sb ₂Se ₃Pipe, and simple fast synthetic this submicron grade square pipe-shaped Sb ₂Se ₃The method of pipe.

Submicron grade square pipe-shaped Sb of the present invention ₂Se ₃, the monocrystalline of genus rhombic system, unit cell parameters is a=11.633

B=11.78

C=3.985

Its structure is the submicron grade square structure, pipe range 10-20 μ m, and the wide 0.5-1 μ of mouth of pipe m, thickness of pipe 100-200nm is along the growth of (001) direction.

Prepare this Sb ₂Se ₃The method of pipe is: at first, at room temperature be 2: 3 SbCl with weight ratio ₃And Na ₂SeO ₃Join in the glycerol, magnetic agitation 0.5-2 hour, put into microwave reactor and heat 8-10min; After the cooling, product is alternately cleaned repeatedly with the second alcohol and water, in vacuum drying oven, promptly got submicron order Sb after the drying ₂Se ₃The four directions pipe.

As above-mentioned preparation method's further improvement, the operating frequency of microwave reactor is preferably 2.45GHz, power is 800W.And microwave reactor preferably adopts 40s work, the circulation heating mode that 60s stops.

Utilize measurement of ultraviolet-visible spectrophotometer gained Sb ₂Se ₃The energy gap of submicron four directions pipe is 1.161eV, with Sb in the document ₂Se ₃The energy gap numerical value of nanostructure such as nanometer rod, nano wire is consistent.The Sb of this explanation present method gained ₂Se ₃The submicron grade square pipe can show the performance of certain nano structural material too.

The invention has the beneficial effects as follows:

(1) Sb of the present invention ₂Se ₃Regular, the big or small homogeneous of submicron grade square tubular construction, size is reported in document near nano level;

(2) the energy gap measured value is 1.161eV, can show the performance of certain nano structural material;

(3) Sb of the present invention's proposition ₂Se ₃The preparation method of submicron grade square pipe is easy, and equipment used is simple, and is consuming time extremely short, can realize a large amount of preparations in the short period of time, is convenient to suitability for industrialized production.

Description of drawings

Fig. 1 is by being synthesized Sb ₂Se ₃XRD figure spectrum.

Fig. 2 is the synthetic Sb of microwave heating 8min institute ₂Se ₃The stereoscan photograph of submicron grade square pipe.

Fig. 3 is the synthetic Sb of microwave heating 10min institute ₂Se ₃The stereoscan photograph of submicron grade square pipe.

Fig. 4 is Sb ₂Se ₃The transmission electron microscope photo of submicron grade square pipe.

Fig. 5 is Sb ₂Se ₃The selected area electron diffraction photo of submicron grade square pipe.

Fig. 6 is Sb ₂Se ₃The diffuse-reflectance collection of illustrative plates of submicron grade square pipe.

Fig. 7 for calculate by the diffuse scattering collection of illustrative plates the collection of illustrative plates of calculating energy gap.

Embodiment

Further specify the present invention below in conjunction with drawings and Examples, wherein the part preparation condition only is the explanation as typical case, is not limitation of the invention.

Embodiment 1

Under the room temperature, with load weighted 0.5mmol SbCl ₃With 0.75mmol Na ₂SeO ₃, adding fills in the container of 15mL glycerol liquid, and magnetic agitation is after 0.5 hour, and putting into operating frequency is that 2.45GHz, power are the microwave reactor of 800W, and reactor adopts 40s work, the circulation heating mode that 60s stops, microwave heating 8min.After the cooling, alternately clean dry 12h under 60 ℃ in the vacuum drying oven repeatedly with the second alcohol and water.

Fig. 1 is by being synthesized Sb ₂Se ₃XRD figure spectrum.All diffraction peaks and lattice parameter are a=11.633

B=11.780

And=3.985

Rhombic system Sb ₂Se ₃The diffraction peak unanimity.The synthetic Sb of institute of the present invention is described ₂Se ₃Be pure phase.

Fig. 2 is microwave heating 8min synthetic Sb ₂Se ₃The field emission scanning electron microscope photo of submicron grade square pipe.From the photo synthetic Sb of institute as can be seen ₂Se ₃Pipe is tetragonal, pipe range 10-20 μ m, the wide 0.5-1 μ of mouth of pipe m, thickness of pipe 100-200nm.

Fig. 4 is Sb ₂Se ₃The transmission electron microscope photo of submicron grade square pipe.Can confirm synthetic Sb of the present invention from photo ₂Se ₃Be tubular structure, and present tetragonal.

Fig. 5 is Sb ₂Se ₃The constituency electronics long drive photo of submicron grade square pipe.Diffraction pattern presents regular point diffraction to be arranged, and the synthetic Sb of institute is described ₂Se ₃The submicron grade square pipe is a monocrystalline.Demarcate diffraction pattern, find that crystal is along the growth of (001) direction.

Fig. 6 is Sb ₂Se ₃The diffuse-reflectance collection of illustrative plates of submicron grade square pipe.Collection of illustrative plates is extrapolated Fig. 7 thus, by the slope of Fig. 7 cut-off line part, synthesize Sb ₂Se ₃The energy gap of pipe is 1.161eV.

Embodiment 2

Under the room temperature, with load weighted 0.5mmol SbCl ₃With 0.75mmol Na ₂SeO ₃, adding fills in the container of 15mL glycerol solution, and magnetic agitation is after 1 hour, and putting into operating frequency is that 2.45GHz, power are the microwave reactor of 800W, and reactor adopts 40s work, the circulation heating mode that 60s stops, microwave heating 10min.After the cooling, alternately clean dry 12h under 60 ℃ in the vacuum drying oven repeatedly with the second alcohol and water.

Fig. 3 is microwave heating 10min synthetic Sb ₂Se ₃The field emission scanning electron microscope photo of submicron grade square pipe.From the photo synthetic Sb of institute as can be seen ₂Se ₃Pipe size dimension and the synthetic Sb of microwave heating 8min institute ₂Se ₃Pipe is consistent, but has cracked slightly.

Embodiment 3

Under the room temperature, with load weighted 0.5mmol SbCl ₃With 0.75mmol Na ₂SeO ₃, adding fills in the container of 15mL glycerol solution, and magnetic agitation is after 1 hour, and putting into operating frequency is that 2.45GHz, power are the microwave reactor of 800W, and reactor adopts 40s work, the circulation heating mode that 60s stops, microwave heating 9min.After the cooling, alternately clean repeatedly with the second alcohol and water, dry 12h under 60 ℃ promptly obtains Sb in the vacuum drying oven ₂Se ₃The submicron grade square pipe.

Embodiment 4

Under the room temperature, with load weighted 0.5mmol SbCl ₃With 0.75mmol Na ₂SeO ₃, adding fills in the container of 20mL glycerol solution, and magnetic agitation is after 1 hour, and putting into operating frequency is that 2.45GHz, power are the microwave reactor of 800W, and reactor adopts 40s work, the circulation heating mode that 60s stops, microwave heating 10min.After the cooling, alternately clean repeatedly with the second alcohol and water, dry 12h under 60 ℃ promptly obtains Sb in the vacuum drying oven ₂Se ₃The submicron grade square pipe.

Embodiment 5

Under the room temperature, with load weighted 0.2mmol SbCl ₃With 0.3mmol Na ₂SeO ₃, adding fills in the container of 20mL glycerol solution, and magnetic agitation is after 1 hour, and putting into operating frequency is that 2.45GHz, power are the microwave reactor of 800W, and reactor adopts 40s work, the circulation heating mode that 60s stops, microwave heating 10min.After the cooling, alternately clean repeatedly with the second alcohol and water, dry 12h under 60 ℃ promptly obtains Sb in the vacuum drying oven ₂Se ₃The submicron grade square pipe.

Claims

1, a kind of submicron grade square pipe-shaped Sb ₂Se ₃, it is characterized in that: this compound belongs to the monocrystalline of rhombic system, and unit cell parameters is a=11.633

B=11.78

C=3.985 Its structure is the submicron grade square structure, pipe range 10-20 μ m, and the wide 0.5-1 μ of mouth of pipe m, thickness of pipe 100-200nm is along the growth of (001) direction.

2, the described submicron grade square pipe-shaped Sb of claim 1 ₂Se ₃The preparation method, it is characterized in that may further comprise the steps: at first, at room temperature be 2: 3 SbCl with the amount of substance ratio ₃And Na ₂SeO ₃Join in the glycerol liquid, magnetic agitation 0.5-2 hour, put into microwave reactor and heat 8-10min; After the cooling, product is alternately cleaned repeatedly with the second alcohol and water, in vacuum drying oven, promptly got submicron order Sb after the drying ₂Se ₃The four directions pipe.

3, submicron grade square pipe-shaped Sb according to claim 2 ₂Se ₃The preparation method, the operating frequency that it is characterized in that microwave reactor is that 2.45GHz, power are 800W.

4, according to claim 2 or 3 described submicron grade square pipe-shaped Sb ₂Se ₃The preparation method, it is characterized in that microwave reactor adopts 40s work, the circulation heating mode that 60s stops.