CN105382254B - A kind of Bi2Te3‑Sb2Te3Nuclear shell structure nano line and preparation method thereof - Google Patents
A kind of Bi2Te3‑Sb2Te3Nuclear shell structure nano line and preparation method thereof Download PDFInfo
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- CN105382254B CN105382254B CN201510746190.6A CN201510746190A CN105382254B CN 105382254 B CN105382254 B CN 105382254B CN 201510746190 A CN201510746190 A CN 201510746190A CN 105382254 B CN105382254 B CN 105382254B
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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
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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
- B22F1/05—Metallic powder characterised by the size or surface area of the particles
- B22F1/054—Nanosized particles
- B22F1/0547—Nanofibres or nanotubes
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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
- 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 kind of Bi2Te3‑Sb2Te3Nuclear shell structure nano line and preparation method thereof, the nano wire is with Bi2Te3For kernel, Bi2Te3External sheath has Sb2Te3Layer；A diameter of 10~50nm of the nano wire, length is 2 20 μm.Using glucose, sucrose or alginic acid as reducing agent, prepared using two step hydro-thermal reactions, prepare the less Te nano wires of diameter in acid condition first as template, then reduction Bi ions and Sb ions prepare Bi in the basic conditions2Te3‑Sb2Te3Nano wire.Environmental protection, reaction condition is gentle, can effectively control course of reaction.Bi prepared by the present invention2Te3‑Sb2Te3Nano wire has special heterogeneous core shell structure, improves its thermoelectricity capability, and the application in thermoelectricity field above shows the potentiality of desirable.
Description
Technical field
The present invention relates to thermoelectric material and its preparing technical field, more particularly to a kind of Bi2Te3-Sb2Te3Core shell structure is received
Rice noodles and preparation method thereof.
Background technology
Thermoelectric material is that a kind of carrier transport by solid realizes the function that heat energy and electric energy are directly mutually changed
Material.The dimension of material is reduced, energy state density and increased phon scattering can be improved, so as to improve conducting material thermoelectricity performance.Low-dimensional
Nano material such as quantum dot, superlattices, nano wire and micro-nano composite are the focus directions of thermoelectric material area research.
Semiconductor nanowires, due to its unique structure and property, may apply in various energy conversion devices.It is theoretical
Research shows the reduction of quantum constraint effect and thermal conductivity caused by the dimension limitation due to nano wire, semiconductor nanowires thermoelectricity
The efficiency of material can significantly improve (L.D.Hicks and M.S.Dresselhaus, Phys.Rev.B, 1993,47,
16631-16634).Experimentally thermal conductivity is significantly reduced for nano wire to be extensively examined, but experimentally for nanometer
Line improves electric property and is rarely reported simultaneously.Therefore, the nano wire of special construction is prepared, such as nucleocapsid heterojunction structure can be adjusted
Band structure, so as to be expected to further improve the thermoelectricity capability of material.Therefore Bi2Te3-Sb2Te3Nuclear shell structure nano line and its
Development and application of the preparation method to thermoelectricity nano-device has great importance.So far Bi is not found2Te3-Sb2Te3Nucleocapsid knot
The relevant report of structure nano wire and preparation method thereof.
On the other hand, in existing preparation Bi2Te3In 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, environment-friendly reducing agent replaces the reduction that those are poisonous
Agent, this more meets " green " synthesis strategy.The organic reducing agents such as glucose, sucrose or alginic acid, reaction condition is gentle, Neng Gouyou
Effect control course of reaction, prepares the nano material of special construction.
The content of the invention
For Shortcomings in the prior art, the invention provides a kind of Bi2Te3-Sb2Te3Nuclear shell structure nano line and its
Preparation method, using simple two one-step hydrothermal, first under lower temperature conditions synthesize Te nano wires, then using Te nano wires as
Template, has synthesized Bi at a higher temperature2Te3-Sb2Te3The nano wire of core shell structure.
The present invention is to realize above-mentioned technical purpose by following technological means.
A kind of Bi2Te3-Sb2Te3Nuclear shell structure nano line, it is characterised in that the nano wire is with Bi2Te3For kernel,
Bi2Te3External sheath has Sb2Te3Layer.
Preferably, a diameter of 10~50nm of the nano wire, length is 2-20 μm.
The Bi2Te3-Sb2Te3The preparation method of nuclear shell structure nano line, is prepared, its feature using two step hydro-thermal reactions
It is, comprises the following steps：
(1) compound of the element containing Te, reducing agent are added in deionized water, add acid-conditioning solution H+Concentration is
0.1~0.2mol/L, it is to be mixed it is uniform after pour into heating response in the hydrothermal reaction kettle that liner is polytetrafluoroethylene (PTFE) and prepare Te and receive
Rice noodles, reaction temperature is 120-180 DEG C, and the reaction time is 4~10h；
(2) reactor of step (1) is naturally cooled to after room temperature, in reaction solution add disodium ethylene diamine tetraacetate and
Reducing agent dissolves, according to the Bi of required synthesisxSb2-xTe3(0<x<2) stoichiometric proportion determined, adds the change of the element containing Bi
The compound of compound and Sb elements, adds alkali regulation solution O H-Concentration is heating after 0.1~0.4mol/L, sealing reactor
Reaction, reaction temperature is 200-220 DEG C, and the reaction time is 12-24h.Reaction terminate after products therefrom is centrifuged, spend from
Sub- water and absolute ethyl alcohol cyclic washing, collects solid sample drying, that is, obtains Bi2Te3-Sb2Te3Nano wire.
Element compound containing Te in the step (1) is tellurite or telluric acid.
Reducing agent in the step (1) is green non-poisonous glucose, sucrose or alginic acid.
The compound of the element containing Bi is the chloride of the element containing Bi, sulfate or nitrate in the step (2).
The compound of the element containing Sb is the chloride of the element containing Sb, sulfate or nitrate in the step (2).
There is advantages below and effect in the preparation method that the present invention is provided：
(1) preparation method is simple to operate.Due to glucose, the reproducibility of sucrose or brown alga scorbic acid in acid condition
It is weaker, it is necessary to which very high temperature could reduce Sb ions.The present invention uses two-step method, prepare in acid condition first diameter compared with
Small Te nano wires are as template, and then reduction Bi ions and Sb ions prepare Bi in the basic conditions2Te3-Sb2Te3Nanometer
Line, reduces reaction temperature.
(2) reducing agent that the present invention is used is glucose, and the organic reducing agent such as sucrose or alginic acid, reaction condition is gentle,
Course of reaction can be effectively controlled, the nano material of special construction is prepared.
(3) Bi prepared by the present invention2Te3-Sb2Te3Nano wire has special heterogeneous core shell structure, and its kernel is
Bi2Te3, outer layer is Sb2Te3.The method provided using the invention is prepared the thermoelectric material with core shell structure and is expected to improve it
Thermoelectricity capability, the application in thermoelectricity field above shows the potentiality of desirable.
Brief description of the drawings
Fig. 1 is the Bi for preparing in the embodiment of the present invention 12Te3-Sb2Te3The X-ray diffraction (XRD) of nuclear shell structure nano line
Collection of illustrative plates；
Fig. 2 is the Bi for preparing in the embodiment of the present invention 12Te3-Sb2Te3The ESEM (SEM) of nuclear shell structure nano line shines
Piece；
Fig. 3 is the Bi for preparing in the embodiment of the present invention 12Te3-Sb2Te3The transmission electron microscope (TEM) of nuclear shell structure nano line shines
Piece；
Fig. 4 is the Bi for preparing in the embodiment of the present invention 12Te3-Sb2Te3The high-resolution-ration transmission electric-lens of nuclear shell structure nano line
(HR-TEM) photo；
Fig. 5 is the Bi for preparing in the embodiment of the present invention 12Te3-Sb2Te3The energy dispersion X-ray light of nuclear shell structure nano line
Spectrometer (EDX) element Surface scan figure.
Embodiment
Below in conjunction with the accompanying drawings and specific embodiment the present invention is further illustrated, but protection scope of the present invention is simultaneously
Not limited to this.
Embodiment 1：
(1) 0.375mmol K2TeO3It is added to 0.2g glucose in deionized water, adds hydrochloric acid conditioning solution H+
Concentration is 0.2mol/L, and stirring and dissolving uniformly obtains 12mL precursor solutions, then moves into the reaction of 16mL polytetrafluoroethyllining linings
In kettle, baking oven, 150 DEG C of insulation 8h are put into.
(2) after step (1) reaction completion is cooled to room temperature, reactor is opened, 0.186g second is added in reaction solution
Edetate disodium and 0.3g glucose, by BixSb2-xTe3(x=1) stoichiometric proportion determined by, adds 0.125mmol
BiCl3、0.125mmol SbCl3, finally adding NaOH makes the OH of solution-Concentration is 0.2mol/L, after being sufficiently stirred for, will be anti-
Answer kettle to seal and be put into baking oven, 220 DEG C of insulation 20h.
(3) product is centrifuged, with deionized water and absolute ethyl alcohol cyclic washing 3-5 times, collects solid sample drying.
Fig. 1 is the XRD spectrum that this example prepares sample, it can be seen that the structure with two-phase of product, respectively Bi2Te3
And Sb2Te3, exist without other dephasigns.Fig. 2 is the SEM photograph for preparing sample, it can be seen that product for single shape
Nano wire, and nanowire size is uniform, diameter is about 40nm, length more than 2 μm.Fig. 3 is the TEM photos for preparing sample, can be with
Find out Bi2Te3-Sb2Te3One layer of organic matter is surrounded by outside nano wire, the organic matter can have with dimethylformamide (DMF) etc.
Machine solution is removed, and obtains single Bi2Te3-Sb2Te3Nano wire.Fig. 4 is Bi2Te3-Sb2Te3The HR-TEM photos of nano wire, can
To see that nanowire has two different (015) high preferred orientations in interior core with outer layer, core shell structure is formed.Fig. 5 is energy dispersion X
Ray spectrometer (EDX) element Surface scan figure, it was demonstrated that prepared Bi2Te3-Sb2Te3Nano wire has core shell structure, its kernel
For Bi2Te3, outer layer is Sb2Te3。
Embodiment 2：
(1) 0.375mmol K2TeO3It is added to 0.2g sucrose in deionized water, adds hydrochloric acid conditioning solution H+It is dense
Spend for 0.1mol/L, stirring and dissolving uniformly obtains 12mL precursor solutions, then moves into the reactor of 16mL polytetrafluoroethyllining linings
In, it is put into baking oven, 120 DEG C of insulation 10h.
(2) after step (1) reaction completion is cooled to room temperature, reactor is opened, 0.186g second is added in reaction solution
Edetate disodium and 0.3g sucrose, by BixSb2-xTe3(x=1.5) stoichiometric proportion determined by adds in reaction solution
Enter 0.1875mmol BiCl3、0.0625mmol SbCl3, finally adding NaOH makes the OH of solution-Concentration is 0.1mol/L, is filled
Divide after stirring, reactor is sealed and baking oven is put into, 200 DEG C of insulation 12h.
(3) product is centrifuged, with deionized water and absolute ethyl alcohol cyclic washing 3-5 times, collects solid sample drying.
Gained sample is by being characterized as Bi2Te3-Sb2Te3Nano wire.
Embodiment 3：
(1) 0.375mmol Te (OH)4It is added to 0.2g alginic acid in deionized water, adds hydrochloric acid conditioning solution H+
Concentration is 0.1mol/L, and stirring and dissolving uniformly obtains 12mL precursor solutions, then moves into the reaction of 16mL polytetrafluoroethyllining linings
In kettle, baking oven, 180 DEG C of insulation 4h are put into.
(2) after step (1) reaction completion is cooled to room temperature, reactor is opened, 0.186g second is added in reaction solution
Edetate disodium and 0.3g alginic acids, by BixSb2-xTe3(x=0.5) stoichiometric proportion is in reaction solution determined by
Add 0.0625mmol Bi (NO3)3、0.1875mmol Sb(NO3)3, finally adding NaOH makes the OH of solution-Concentration is
0.4mol/L, after being sufficiently stirred for, reactor is sealed and baking oven is put into, 220 DEG C of insulation 24h.
(3) product is centrifuged, with deionized water and absolute ethyl alcohol cyclic washing 3-5 times, collects solid sample drying.
Gained sample is by being characterized as Bi2Te3-Sb2Te3Nano wire.
For the present invention preferred embodiment, but the present invention is not limited to above-mentioned embodiment to the embodiment, not
In the case of the substantive content of the present invention, any conspicuously improved, replacement that those skilled in the art can make
Or modification belongs to protection scope of the present invention.
Claims (5)
1.Bi2Te3-Sb2Te3The preparation method of nuclear shell structure nano line, the nano wire is with Bi2Te3For kernel, Bi2Te3Outer layer
It is coated with Sb2Te3Layer, is prepared, it is characterised in that comprise the following steps using two step hydro-thermal reactions：
(1) compound of the element containing Te, reducing agent are added in deionized water, adding acid-conditioning solution makes H+Concentration be 0.1~
0.2mol/L, it is to be mixed it is uniform after pour into the hydrothermal reaction kettle that liner is polytetrafluoroethylene (PTFE), be heated to 120~180 DEG C of reactions 4
~10h prepares Te nano wires；
(2) reactor of step (1) is naturally cooled to after room temperature, and disodium ethylene diamine tetraacetate and reduction are added in reaction solution
Agent, according to the Bi of required synthesisxSb2-xTe3(0<x<2) stoichiometric proportion determined, adds the compound and Sb of the element containing Bi
The compound of element, adding alkali regulation solution makes OH-Concentration is 0.1~0.4mol/L, and 200- is heated to after sealing reactor
220 DEG C of reaction 12-24h, reaction centrifuges products therefrom after terminating, with deionized water and absolute ethyl alcohol cyclic washing, receives
Collect solid sample drying, that is, obtain Bi2Te3-Sb2Te3Nano wire.
2. Bi according to claim 12Te3-Sb2Te3The preparation method of nuclear shell structure nano line, it is characterised in that described
Element compound containing Te in step (1) is tellurite.
3. Bi according to claim 12Te3-Sb2Te3The preparation method of nuclear shell structure nano line, it is characterised in that described
Reducing agent in step (1) is glucose, sucrose or alginic acid.
4. Bi according to claim 12Te3-Sb2Te3The preparation method of nuclear shell structure nano line, it is characterised in that：It is described
The compound of the element containing Bi is chloride, sulfate or the nitrate of the element containing Bi in step (2).
5. Bi according to claim 12Te3-Sb2Te3The preparation method of nuclear shell structure nano line, it is characterised in that：It is described
The compound of the element containing Sb is chloride, sulfate or the nitrate of the element containing Sb in step (2).
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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 |
| CN109950138B (en) * | 2019-04-11 | 2020-11-13 | 广东工业大学 | Nano-pillar array heterojunction and preparation method thereof |
| 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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| CN103647016A (en) * | 2013-12-12 | 2014-03-19 | 中国科学院半导体研究所 | Preparation method for thermo-electric device based on core shell structure |
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| US7767564B2 (en) * | 2005-12-09 | 2010-08-03 | Zt3 Technologies, Inc. | Nanowire electronic devices and method for producing the same |
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| JP2005093454A (en) * | 2003-09-11 | 2005-04-07 | Yamaha Corp | Thermoelectric material and its manufacturing method |
| CN101214548A (en) * | 2007-12-27 | 2008-07-09 | 杭州电子科技大学 | Method for preparing core-shell structure nano pyroelectric material |
| CN101237018A (en) * | 2008-02-26 | 2008-08-06 | 杭州电子科技大学 | Nano thermal electric material with coaxial cable structure and its making method |
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