CN105382254A - Bi2Te3-Sb2Te3 core-shell structure nanometer wire and preparing method thereof - Google Patents

Bi2Te3-Sb2Te3 core-shell structure nanometer wire and preparing method thereof Download PDF

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Publication number
CN105382254A
CN105382254A CN201510746190.6A CN201510746190A CN105382254A CN 105382254 A CN105382254 A CN 105382254A CN 201510746190 A CN201510746190 A CN 201510746190A CN 105382254 A CN105382254 A CN 105382254A
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shell structure
nanometer wire
nuclear shell
reaction
bi2te3
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CN105382254B (en
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糜建立
冯宏庆
董明东
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Jiangsu University
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Jiangsu University
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • B22F1/17—Metallic particles coated with metal
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • B22F1/05—Metallic powder characterised by the size or surface area of the particles
    • B22F1/054—Nanosized particles
    • B22F1/0547—Nanofibres or nanotubes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F9/00—Making metallic powder or suspensions thereof
    • B22F9/16—Making metallic powder or suspensions thereof using chemical processes
    • B22F9/18—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds
    • B22F9/24—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from liquid metal compounds, e.g. solutions

Abstract

The invention provides a Bi2Te3-Sb2Te3 core-shell structure nanometer wire and a preparing method thereof. The Bi2Te3 serves as an inner core of the nanometer wire, and the outer layer of the Bi2Te3 is wrapped by a Sb2Te3 layer. The diameter of the nanometer wire is 10-50 nm, and the length of the nanometer wire is 2-20 microns. Glucose or saccharose or alginic acid serves as a reducing agent, two steps of hydrothermal reactions are adopted for preparing, a Te nanometer wire with the small diameter is prepared under the acidic condition to serve as a template, and ions Bi and ions Sb are reduced under the alkaline condition to prepare the Bi2Te3-Sb2Te3 nanometer wire. Environment friendliness is achieved, the reaction condition is moderate, and the reaction process can be effectively controlled. The prepared Bi2Te3-Sb2Te3 nanometer wire has the special neterogeny core-shell structure, the thermoelectric properties of the nanometer wire are improved, and hopeful potential is shown in the application to the thermoelectricity field.

Description

A kind of Bi 2te 3-Sb 2te 3nuclear shell structure nano line and preparation method thereof
Technical field
The present invention relates to thermoelectric material and preparing technical field thereof, particularly relate to a kind of Bi 2te 3-Sb 2te 3nuclear shell structure nano line and preparation method thereof.
Background technology
Thermoelectric material a kind ofly realizes by the carrier transport in solid the functional material that heat energy and electric energy directly change mutually.Reduce the dimension of material, the phon scattering of energy state density and increase can be improved, thus improve conducting material thermoelectricity performance.Low-dimension nano material is as quantum dot, and superlattices, nano wire and micro-nano composite are the focus directions of thermoelectric material area research.
Semiconductor nanowires, due to the structures and characteristics of its uniqueness, can be applied in various energy conversion device.Theoretical research shows that the dimension due to nano wire limits the reduction of quantum constraint effect and the thermal conductivity caused, the efficiency of semiconductor nanowires thermoelectric material can significantly improve (L.D.HicksandM.S.Dresselhaus, Phys.Rev.B, 1993,47,16631-16634).Experimentally thermal conductivity is significantly reduced for nano wire to be extensively examined, but experimentally improve electric property for nano wire rarely has report simultaneously.Therefore, prepare the nano wire of special construction, as nucleocapsid heterojunction structure, can band structure be regulated, thus be expected to the thermoelectricity capability improving material further.Therefore Bi 2te 3-Sb 2te 3the development and application of nuclear shell structure nano line and preparation method thereof to thermoelectricity nano-device has great importance.So far Bi is not found 2te 3-Sb 2te 3the relevant report of nuclear shell structure nano line and preparation method thereof.
On the other hand, at existing preparation Bi 2te 3in the method for based nano-material, reducing agent used is mostly hydrazine hydrate, sodium borohydride, or the poisonous reducing agent such as DMF, therefore a kind of nontoxic, eco-friendly reducing agent reducing agent of replacing those poisonous, this more meets " green " synthesis strategy.The organic reducing agents such as glucose, sucrose or alginic acid, reaction condition is gentle, effectively can control course of reaction, prepare the nano material of special construction.
Summary of the invention
For Shortcomings in prior art, the invention provides a kind of Bi 2te 3-Sb 2te 3nuclear shell structure nano line and preparation method thereof, adopts simple two one-step hydrothermals, first under lower temperature conditions, synthesizes Te nano wire, then with Te nano wire for template, has synthesized Bi at a higher temperature 2te 3-Sb 2te 3the nano wire of nucleocapsid structure.
The present invention realizes above-mentioned technical purpose by following technological means.
A kind of Bi 2te 3-Sb 2te 3nuclear shell structure nano line, is characterized in that, described nano wire is with Bi 2te 3for kernel, Bi 2te 3external sheath has Sb 2te 3layer.
Preferably, the diameter of described nano wire is 10 ~ 50nm, and length is 2-20 μm.
Described Bi 2te 3-Sb 2te 3the preparation method of nuclear shell structure nano line, adopts two step hydro-thermal reaction preparations, it is characterized in that, comprise the following steps:
(1) by joining in deionized water containing the compound of Te element, reducing agent, acid-conditioning solution H is added +concentration is 0.1 ~ 0.2mol/L, to be mixed evenly after to pour liner into be add thermal response in the hydrothermal reaction kettle of polytetrafluoroethylene (PTFE) to prepare Te nano wire, reaction temperature is 120-180 DEG C, and the reaction time is 4 ~ 10h;
(2), after the reactor of step (1) naturally cools to room temperature, in reaction solution, disodium ethylene diamine tetraacetate and reducing agent dissolving is added, according to the Bi of required synthesis xsb 2-xte 3(0<x<2) stoichiometric proportion determined, adds the compound of compound containing Bi element and Sb element, then adds alkali and regulate solution O H -concentration is 0.1 ~ 0.4mol/L, adds thermal response after sealed reactor, and reaction temperature is 200-220 DEG C, and the reaction time is 12-24h.By products therefrom centrifugation, use deionized water and absolute ethyl alcohol cyclic washing after reaction terminates, collect solid sample and dry, namely obtain Bi 2te 3-Sb 2te 3nano wire.
In described step (1) is tellurite or telluric acid containing Te element compound.
Reducing agent in described step (1) is green non-poisonous glucose, sucrose or alginic acid.
Containing chloride, sulfate or nitrate that the compound of Bi element is containing Bi element in described step (2).
Containing chloride, sulfate or nitrate that the compound of Sb element is containing Sb element in described step (2).
There is following advantage and effect in preparation method provided by the invention:
(1) preparation method is simple to operate.Because glucose, sucrose or alginic acid reducing agent reproducibility are in acid condition more weak, need very high temperature could reduce Sb ion.The present invention adopts two-step method, prepares the less Te nano wire of diameter first in acid condition as template, and then reduction Bi ion and Sb ion prepare Bi in the basic conditions 2te 3-Sb 2te 3nano wire, reduces reaction temperature.
(2) reducing agent that the present invention uses is glucose, the organic reducing agent such as sucrose or alginic acid, and reaction condition is gentle, effectively can control course of reaction, prepare the nano material of special construction.
(3) Bi for preparing of the present invention 2te 3-Sb 2te 3nano wire has special heterogeneous nucleocapsid structure, and its kernel is Bi 2te 3, skin is Sb 2te 3.The thermoelectric material that the method preparation utilizing this invention to provide has nucleocapsid structure is expected to improve its thermoelectricity capability, and the application in thermoelectricity field shows the potentiality of desirable.
Accompanying drawing explanation
Fig. 1 is the Bi of preparation in the embodiment of the present invention 1 2te 3-Sb 2te 3x-ray diffraction (XRD) collection of illustrative plates of nuclear shell structure nano line;
Fig. 2 is the Bi of preparation in the embodiment of the present invention 1 2te 3-Sb 2te 3eSEM (SEM) photo of nuclear shell structure nano line;
Fig. 3 is the Bi of preparation in the embodiment of the present invention 1 2te 3-Sb 2te 3transmission electron microscope (TEM) photo of nuclear shell structure nano line;
Fig. 4 is the Bi of preparation in the embodiment of the present invention 1 2te 3-Sb 2te 3high-resolution-ration transmission electric-lens (HR-TEM) photo of nuclear shell structure nano line;
Fig. 5 is the Bi of preparation in the embodiment of the present invention 1 2te 3-Sb 2te 3energy dispersion X-ray spectrometer (EDX) the element Surface scan figure of nuclear shell structure nano line.
Detailed description of the invention
Below in conjunction with accompanying drawing and specific embodiment, the present invention is further illustrated, but protection scope of the present invention is not limited to this.
Embodiment 1:
(1) K of 0.375mmol 2teO 3be added in deionized water with the glucose of 0.2g, add hydrochloric acid conditioning solution H +concentration is 0.2mol/L, and stirring and dissolving evenly obtains 12mL precursor solution, then moves in 16mL teflon-lined reactor, puts into baking oven, 150 DEG C of insulation 8h.
(2) after step (1) has been reacted and is cooled to room temperature, open reactor, in reaction solution, add 0.186g disodium ethylene diamine tetraacetate and 0.3g glucose, by Bi xsb 2-xte 3(x=1) determined stoichiometric proportion, adds 0.125mmolBiCl 3, 0.125mmolSbCl 3, finally add the OH that NaOH makes solution again -concentration is 0.2mol/L, after fully stirring, is sealed by reactor and puts into baking oven, 220 DEG C of insulation 20h.
(3) by product centrifugation, with deionized water and absolute ethyl alcohol cyclic washing 3-5 time, collect solid sample oven dry.
Fig. 1 is the XRD collection of illustrative plates that this example prepares sample, can find out the structure with two-phase of product, be respectively Bi 2te 3and Sb 2te 3, and there is no other dephasigns.Fig. 2 is the SEM photo preparing sample, and can find out the nano wire for single shape of product, and nanowire size is even, diameter is about 40nm, length is greater than 2 μm.Fig. 3 is the TEM photo preparing sample, can find out Bi 2te 3-Sb 2te 3be surrounded by one deck organic matter outside nano wire, this organic matter can use the organic solutions such as dimethyl formamide (DMF) to remove, and obtains single Bi 2te 3-Sb 2te 3nano wire.Fig. 4 is Bi 2te 3-Sb 2te 3the HR-TEM photo of nano wire, can see that nanowire has two difference (015) high preferred orientations at kernel and skin, forms nucleocapsid structure.Fig. 5 is energy dispersion X-ray spectrometer (EDX) element Surface scan figure, the Bi prepared by proving 2te 3-Sb 2te 3nano wire has nucleocapsid structure, and its kernel is Bi 2te 3, skin is Sb 2te 3.
Embodiment 2:
(1) K of 0.375mmol 2teO 3be added in deionized water with the sucrose of 0.2g, add hydrochloric acid conditioning solution H +concentration is 0.1mol/L, and stirring and dissolving evenly obtains 12mL precursor solution, then moves in 16mL teflon-lined reactor, puts into baking oven, 120 DEG C of insulation 10h.
(2) after step (1) has been reacted and is cooled to room temperature, open reactor, in reaction solution, add 0.186g disodium ethylene diamine tetraacetate and 0.3g sucrose, by Bi xsb 2-xte 3(x=1.5) determined stoichiometric proportion adds 0.1875mmolBiCl in reaction solution 3, 0.0625mmolSbCl 3, finally add the OH that NaOH makes solution again -concentration is 0.1mol/L, after fully stirring, is sealed by reactor and puts into baking oven, 200 DEG C of insulation 12h.
(3) by product centrifugation, with deionized water and absolute ethyl alcohol cyclic washing 3-5 time, collect solid sample oven dry.
Gained sample is by being characterized by Bi 2te 3-Sb 2te 3nano wire.
Embodiment 3:
(1) Te (OH) of 0.375mmol 4be added in deionized water with the alginic acid of 0.2g, add hydrochloric acid conditioning solution H +concentration is 0.1mol/L, and stirring and dissolving evenly obtains 12mL precursor solution, then moves in 16mL teflon-lined reactor, puts into baking oven, 180 DEG C of insulation 4h.
(2) after step (1) has been reacted and is cooled to room temperature, open reactor, in reaction solution, add 0.186g disodium ethylene diamine tetraacetate and 0.3g alginic acid, by Bi xsb 2-xte 3(x=0.5) determined stoichiometric proportion adds 0.0625mmolBi (NO in reaction solution 3) 3, 0.1875mmolSb (NO 3) 3, finally add the OH that NaOH makes solution again -concentration is 0.4mol/L, after fully stirring, is sealed by reactor and puts into baking oven, 220 DEG C of insulation 24h.
(3) by product centrifugation, with deionized water and absolute ethyl alcohol cyclic washing 3-5 time, collect solid sample oven dry.
Gained sample is by being characterized by Bi 2te 3-Sb 2te 3nano wire.
Described embodiment is preferred embodiment of the present invention; but the present invention is not limited to above-mentioned embodiment; when not deviating from flesh and blood of the present invention, any apparent improvement that those skilled in the art can make, replacement or modification all belong to protection scope of the present invention.

Claims (7)

1. a Bi 2te 3-Sb 2te 3nuclear shell structure nano line, is characterized in that, described nano wire is with Bi 2te 3for kernel, Bi 2te 3external sheath has Sb 2te 3layer.
2. Bi according to claim 1 2te 3-Sb 2te 3nuclear shell structure nano line, is characterized in that, the diameter of described nano wire is 10 ~ 50nm, and length is 2-20 μm.
3. Bi according to claim 1 2te 3-Sb 2te 3the preparation method of nuclear shell structure nano line, adopts two step hydro-thermal reaction preparations, it is characterized in that, comprise the following steps:
(1) by joining in deionized water containing the compound of Te element, reducing agent, adding acid-conditioning solution and making H +concentration is 0.1 ~ 0.2mol/L, to be mixed evenly after to pour liner into be in the hydrothermal reaction kettle of polytetrafluoroethylene (PTFE), be heated to 120 ~ 180 DEG C of reaction 4 ~ 10h and prepare Te nano wire;
(2) after the reactor of step (1) naturally cools to room temperature, in reaction solution, disodium ethylene diamine tetraacetate and reducing agent is added, according to the Bi of required synthesis xsb 2-xte 3(0<x<2) stoichiometric proportion determined, adds the compound of compound containing Bi element and Sb element, then adds alkali and regulate solution to make OH -concentration is 0.1 ~ 0.4mol/L, is heated to 200-220 DEG C of reaction 12-24h after sealed reactor, by products therefrom centrifugation, with deionized water and absolute ethyl alcohol cyclic washing, collect solid sample and dry, namely obtain Bi after reaction terminates 2te 3-Sb 2te 3nano wire.
4. Bi according to claim 3 2te 3-Sb 2te 3the preparation method of nuclear shell structure nano line, is characterized in that, in described step (1) is tellurite or telluric acid containing Te element compound.
5. Bi according to claim 3 2te 3-Sb 2te 3the preparation method of nuclear shell structure nano line, is characterized in that, the reducing agent in described step (1) is glucose, sucrose or alginic acid.
6. Bi according to claim 3 2te 3-Sb 2te 3the preparation method of nuclear shell structure nano line, is characterized in that: be containing the chloride of Bi element, sulfate or nitrate containing the compound of Bi element in described step (2).
7. Bi according to claim 3 2te 3-Sb 2te 3the preparation method of nuclear shell structure nano line, is characterized in that: be containing the chloride of Sb element, sulfate or nitrate containing the compound of Sb element in described step (2).
CN201510746190.6A 2015-11-05 2015-11-05 A kind of Bi2Te3‑Sb2Te3Nuclear shell structure nano line and preparation method thereof Expired - Fee Related CN105382254B (en)

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Cited By (3)

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CN107546317A (en) * 2017-09-04 2018-01-05 江西科技师范大学 Flexible compound thermal electric film and preparation method thereof
CN109950138A (en) * 2019-04-11 2019-06-28 广东工业大学 A kind of nanometer column array heterojunction and preparation method thereof
CN113697780A (en) * 2021-10-20 2021-11-26 哈尔滨工业大学 Preparation method of pH-regulated bismuth telluride nanowire

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JP2005093454A (en) * 2003-09-11 2005-04-07 Yamaha Corp Thermoelectric material and its manufacturing method
US20100270617A1 (en) * 2005-12-09 2010-10-28 Zt3 Technologies, Inc. Nanowire electronic devices and method for producing the same
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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107546317A (en) * 2017-09-04 2018-01-05 江西科技师范大学 Flexible compound thermal electric film and preparation method thereof
CN109950138A (en) * 2019-04-11 2019-06-28 广东工业大学 A kind of nanometer column array heterojunction and preparation method thereof
CN113697780A (en) * 2021-10-20 2021-11-26 哈尔滨工业大学 Preparation method of pH-regulated bismuth telluride nanowire
CN113697780B (en) * 2021-10-20 2022-12-16 哈尔滨工业大学 Preparation method of pH-regulated bismuth telluride nanowire

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