CN101602495A - A kind of lead telluride nano crystal and the brilliant preparation method of micron - Google Patents
A kind of lead telluride nano crystal and the brilliant preparation method of micron Download PDFInfo
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- CN101602495A CN101602495A CNA2009100544550A CN200910054455A CN101602495A CN 101602495 A CN101602495 A CN 101602495A CN A2009100544550 A CNA2009100544550 A CN A2009100544550A CN 200910054455 A CN200910054455 A CN 200910054455A CN 101602495 A CN101602495 A CN 101602495A
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Abstract
The present invention relates to a kind of lead telluride nano crystal and the brilliant preparation method of micron, belong to field of thermoelectric material technique.This method is a raw material with the soluble salt of lead, the compound that contains tellurium, is reductive agent with alkali-metal hydroborate, adopts mixed hydroxides as reaction medium, and in 170-200 ℃ of reaction 0.5-12 hour, it was nanocrystalline brilliant with micron to have prepared PbTe under the normal pressure.The characteristics that preparation method involved in the present invention has equipment and process is simple, with low cost, speed of response is fast, and be easy to carry out suitability for industrialized production.The present invention can obtain the nano level and the micron order PbTe product of different-shape by simple controlling reaction time.The product good crystallinity that is obtained, cleaning surfaces and smoother have potential using value at aspects such as nanometer and minisize thermoelectric preparation of devices.
Description
Technical field
The present invention relates to the preparation of semi-conductor thermoelectric material, relate to lead telluride nano crystal and the brilliant preparation method of micron.
Background technology
Along with environment and energy problem become increasingly conspicuous, development environment close friend's cleaning new energy has caused the great attention of various countries scientific circles and engineering circle.Thermoelectric material is the new function material that a class utilizes Seebeck (Seebeck) effect and Peltier (Peltier) effect that heat energy and electric energy are changed mutually.The application of thermo-electric device does not need to use drive disk assembly, and noiseless, nothing dump thing during work, environment is not polluted, and this material property are reliable, and long service life is a kind of environment-friendly material with wide application prospect.At present, thermoelectric material fields such as spacecraft power generation assembly, movable small power generation assembly, Small Refrigerating Equipment and portable refrigerating box between deep space have obtained using comparatively widely, also have the potential significant application value aspect waste heat, the waste-heat power generation simultaneously.
PbTe is the IV-VI group iii v compound semiconductor material, has high melt point (1196K), its crystalline structure belongs to the NaCl structure, energy gap narrower (about 0.3eV), have isotropic structure, high crystal symmetry, low advantages such as lattice thermal conductivity, a kind of good in warm electric material.Nearest discovers, adopts nanotechnology, by reducing the material dimension, as existing thermoelectric material is made two-dimensional nano film, one-dimensional nano line or zero-dimensional quantum dots, can increase substantially the ZT value of material.Nano material technology has been opened up another new way for the thermoelectric material that development has high conversion efficiency of thermoelectric.The preparation of PbTe nano material has been subjected to investigator's extensive concern, and the preparation method of report comprises methods such as hydrothermal method, electrochemical process, template, chemical gas phase be synthetic at present.These preparation method's relative complex, and need some utility appliance, cost is higher.
Summary of the invention
The purpose of this invention is to provide a kind of nanometer and micron order lead telluride preparation methods.
Preparation method among the present invention comprises following steps:
1) batching: in Pb and Te atomic ratio is the raw material that 1: 1 ratio takes by weighing 0.6-3 mmole lead and tellurium respectively, its adding is filled in the reaction vessel of 10-20 gram mixed hydroxides, take by weighing the reductive agent of 4.5-22.5 mmole simultaneously, its adding is filled in another reaction vessel of 10-20 gram mixed hydroxides;
2) heating and melting: the container that will fill reactant places heating installation preheating 1-2 hour that is heated to 170-200 ℃, the mixed base in the reaction vessel is melted fully, and reactant is dispersed in the mixed base liquation;
3) mix and carry out isothermal reaction:, make it under temperature constant state, continue reaction 0.5-12 hour then the reactant uniform mixing in above-mentioned two reaction vessels;
4) cooling: after reaction proceeds to setting-up time, reaction vessel is cooled to room temperature;
5) washing: the mixture washing that will contain product and mixed base is extremely neutral, and obtains sample through centrifugation;
6) oven dry: will wash afterwards that products therefrom carries out drying in vacuum drying oven, get final product final product.
The raw material of the lead described in the present invention is lead nitrate, plumbic acetate or lead chloride; The compound that contains tellurium comprises tellurite, tellurium dioxide, tellurium potassium or tellurium sodium; Reductive agent is alkali-metal hydroborate, is preferably POTASSIUM BOROHYDRIDE; Described mixed hydroxides is meant the mixture of sodium hydroxide and potassium hydroxide, and the mass percent of the shared mixed hydroxides of sodium hydroxide is 45-55%; Preferably, wherein the mass ratio of sodium hydroxide and potassium hydroxide is 51.5: 48.5.
Reaction vessel among the present invention is a tetrafluoroethylene material container; But described heating installation is the baking oven of accurate temperature controlling.
Cleaning step described in the present invention is that the mixed base that adopts cold or hot deionized water will be solidified with product fully dissolves, and suspension separates through whizzer, uses the deionized water repetitive scrubbing until neutrality products therefrom, uses absolute ethanol washing 2-4 time at last.Described centrifugal speed is 3000-4000 rev/min.
Vacuum drying treatment condition described in the present invention is that vacuum tightness is not higher than 133Pa, and temperature is 50-80 ℃, time 5-10 hour.
The present invention is a raw material with the soluble salt of lead, the compound that contains tellurium, with alkali-metal hydroborate is reductive agent, adopt mixed hydroxides as reaction medium, under the normal pressure in 180 ℃ by controlling reaction time, the PbTe that has prepared different-shape is nanocrystalline brilliant with micron.Preparation method involved in the present invention is simple, economical, quick, and is easy to carry out suitability for industrialized production.Institute's synthetic product good crystallinity, purity is higher, and surface cleaning and smooth helps its application in thermo-electric device.
Description of drawings
Fig. 1 is the nanocrystalline x-ray diffraction pattern of PbTe that the present invention produces, and wherein (a) (b) is PbTe standard card JCPDS No.65-0324 for the diffractogram of 0.75 hour products therefrom of reaction.
Fig. 2 be the PbTe powder that produces of the present invention stereoscan photograph and can spectrogram, wherein (a) is reaction 0.75 hour, (b) is reaction 1.5 hours, (c) is reaction 2.5 hours, (d) is the energy spectrum analysis of 2.5 hours gained samples of reaction.
Fig. 3 is the PbTe powder transmission electron microscope photo that the present invention produces, and wherein (a) is reaction 0.75 hour, (b) is reaction 1.5 hours, (c) is reaction 1.75 hours.
Embodiment
The present invention is further illustrated below in conjunction with embodiment.
Embodiment 1
1) takes by weighing 9.7 gram KOH and 10.3 gram NaOH and Sheng respectively and go into the 50ml polytetrafluoroethylcontainer container, then to wherein adding 0.494 gram Pb (NO
3)
2Reach 0.239 gram TeO
2, after mixing container is sealed; Fill to another and to add 0.62 gram reductive agent KBH in the polytetrafluoroethylcontainer container of same quality KOH and NaOH
4, mix and seal.
2) above-mentioned two containers are placed 180 ℃ baking oven preheating 1.5 hours, during rocked reaction vessel about 30 seconds every 20-30 minute, promoting the thawing of mixed base, and reactant is dispersed in the mixed base liquation.
3), make it under 180 ℃ of temperature constant states, continue reaction 45 minutes then with the reactant uniform mixing in above-mentioned two reaction vessels.
4) reaction vessel is taken out from baking oven, in air, naturally cool to room temperature.
5) adopt the mixture that hot deionized water will contain product and mixed base fully to dissolve, suspension was isolated product with whizzer through 5 minutes under 4000 rev/mins speed, products therefrom is reached 7 with the deionized water repetitive scrubbing until pH, use absolute ethanol washing at last 3 times.
6) the back products therefrom will be washed in 70 ℃ vacuum drying oven dry 5 hours, finally the PbTe nanometer powder can be got.
The X-ray diffraction analytical results shows (Fig. 1), and prepared product has the cubic crystal structure of NaCl type, and the product purity height.Scanning electron microscopic observation shows that product is nano-scale particle (Fig. 2 (a)), and through transmission electron microscope observing, product is the isometric particle (Fig. 3 (a)) of 20-40 nanometer.Fig. 3 (a) upper right corner electron diffraction analysis shows that particle is the nanometer monocrystalline particle.
1) takes by weighing 19.4 gram KOH and 20.6 gram NaOH and Sheng respectively and go into the 100ml polytetrafluoroethylcontainer container, then to wherein adding 0.494 gram Pb (NO
3)
2Reach 0.332 gram Na
2TeO
3, after mixing container is sealed; Fill to another and to add 0.62 gram reductive agent KBH in the polytetrafluoroethylcontainer container of same quality KOH and NaOH
4, mix and seal.
2) above-mentioned two containers are placed 180 ℃ baking oven preheating 2 hours, during rocked reaction vessel about 30 seconds every 20-30 minute, promoting the thawing of mixed base, and reactant is dispersed in the mixed base liquation.
3), make it under 180 ℃ of temperature constant states, continue reaction 1 hour then with the reactant uniform mixing in above-mentioned two reaction vessels.
4) reaction vessel is taken out from baking oven, in air, naturally cool to room temperature.
5) mixed base that adopts hot deionized water will be solidified with product fully dissolves, suspension was isolated product with whizzer through 5 minutes under 4000 rev/mins speed, products therefrom is reached 7 with the deionized water repetitive scrubbing until pH, use absolute ethanol washing at last 3 times.
6) the back products therefrom will be washed in 70 ℃ vacuum drying oven dry 5 hours, finally the PbTe nanometer powder can be got.
Gained result and example 1 result are similar.
Embodiment 3
Step is with example 1, and difference only is that the reaction times in the step 3) is 1.5 hours.
Products therefrom pattern and example 1 have bigger difference.Scanning electron microscopic observation shows that product mostly is bar-shaped, flaky nanocrystalline (Fig. 2 (b)) greatly.Transmission electron microscope observing shows the coacervate that includes nano particle in the product, contains a large amount of bar-shaped and flaky nanostructures (Fig. 3 (b)) simultaneously.
Step is with example 1, and difference only is that the reaction times in the step 3) is 1.75 hours.
Products therefrom is monocrystal nano rod, nanometer sheet and nanocubes.Fig. 3 (c) is the more intact PbTe nanometer rod of growth and the transmission electron microscope photo of flaky nanocrystalline, about 200 nanometers of the diameter of nanometer rod wherein, and flaky nanocrystalline thickness is less than 50 nanometers.
Embodiment 5
Step is with example 1, and difference only is that the reaction times in the step 3) is 2.5 hours.
Products therefrom is sheet, prism-shaped and cubic micron crystalline substance.Scanning electron microscopic observation show the brilliant great majority of gained PbTe micron in the form of sheets, prism-shaped and cubic, and surperficial smoother smooth (Fig. 2 (c)).Contain Pb and Te (Fig. 2 (d)) in the EDAX results show sample, and atomic ratio was near 1: 1.
The above-mentioned description to embodiment is can understand and apply the invention for ease of those skilled in the art.The person skilled in the art obviously can easily make various modifications to these embodiment, and needn't pass through performing creative labour being applied in the General Principle of this explanation among other embodiment.Therefore, the invention is not restricted to the embodiment here, those skilled in the art should be within protection scope of the present invention for improvement and modification that the present invention makes according to announcement of the present invention.
Claims (9)
1, a kind of lead telluride nano crystal and the brilliant preparation method of micron is characterized in that, comprise following steps:
1) batching: take by weighing the raw material of lead and tellurium, and its adding is filled in the reaction vessel of mixed hydroxides, take by weighing reductive agent simultaneously, its adding is filled in another reaction vessel of mixed hydroxides;
2) heating and melting: heating is melted the mixed base in the reaction vessel fully, and reactant is dispersed in the mixed base liquation;
3) mix and carry out isothermal reaction:, make it under temperature constant state, continue reaction 0.5-12 hour then the reactant uniform mixing in above-mentioned two reaction vessels;
4) cooling: after reaction proceeds to setting-up time, reaction vessel is cooled to room temperature;
5) washing: reaction product is washed to neutral, and obtain product through centrifugation;
6) oven dry: will wash the back products therefrom and in vacuum drying oven, carry out drying, and promptly obtain final product.
2, preparation method as claimed in claim 1, it is characterized in that: described batching is meant that in Pb and Te atomic ratio be the raw material that 1: 1 ratio takes by weighing 0.6-3 mmole lead and tellurium respectively, its adding is filled in the reaction vessel of 10-20 gram mixed hydroxides, take by weighing the reductive agent of 4.5-22.5 mmole simultaneously, its adding is filled in another reaction vessel of 10-20 gram mixed hydroxides.
3, preparation method as claimed in claim 1 is characterized in that: described heating and melting is meant that the container that will fill reactant places heating installation preheating 1-2 hour that is heated to 170-200 ℃, and the mixed base in the reaction vessel is melted fully.
4, preparation method as claimed in claim 1 is characterized in that: the raw material of described lead is lead nitrate, plumbic acetate or lead chloride; The compound that contains tellurium is tellurite, tellurium dioxide, tellurium potassium or tellurium sodium.
5, preparation method as claimed in claim 1 is characterized in that: described mixed hydroxides is meant the mixture of sodium hydroxide and potassium hydroxide, and the mass percent of the shared mixed hydroxides of sodium hydroxide is 45-55%.
6, preparation method as claimed in claim 1 is characterized in that: described reductive agent is POTASSIUM BOROHYDRIDE or sodium borohydride, carries out in order to react fully, and the add-on of reductive agent can be suitably excessive.
7, preparation method as claimed in claim 1 is characterized in that: described reaction vessel is a tetrafluoroethylene material container; But described heating installation is the baking oven of accurate temperature controlling.
8, preparation method as claimed in claim 1, it is characterized in that: described cleaning step is to adopt the mixture that cold or hot deionized water will contain product and mixed base fully to dissolve, suspension whizzer centrifugation under 3000-4000 rev/min speed, products therefrom is extremely neutral with the deionized water repetitive scrubbing, use absolute ethanol washing 2-4 time at last.
9, preparation method as claimed in claim 1 is characterized in that: described vacuum drying treatment condition is that vacuum tightness is not higher than 133Pa, and temperature is 50-80 ℃, and the time is 5-10 hour.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101973531A (en) * | 2010-05-28 | 2011-02-16 | 重庆大学 | Method for preparing tellurate nanometer materials |
| CN103935968A (en) * | 2014-03-24 | 2014-07-23 | 莫荣 | Method for recovering tellurium from tellurium diethyl dithiocarbamate waste material |
| CN107473189A (en) * | 2017-09-30 | 2017-12-15 | 合肥师范学院 | The preparation method of sea urchin shape nanometer lead telluride and the sea urchin shape nanometer lead telluride being prepared |
| CN108217611A (en) * | 2017-12-29 | 2018-06-29 | 北京航空航天大学 | A kind of preparation method of high natrium doping lead telluride |
-
2009
- 2009-07-07 CN CNA2009100544550A patent/CN101602495A/en active Pending
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101973531A (en) * | 2010-05-28 | 2011-02-16 | 重庆大学 | Method for preparing tellurate nanometer materials |
| CN101973531B (en) * | 2010-05-28 | 2013-03-06 | 重庆大学 | Method for preparing tellurate nanometer materials |
| CN103935968A (en) * | 2014-03-24 | 2014-07-23 | 莫荣 | Method for recovering tellurium from tellurium diethyl dithiocarbamate waste material |
| CN103935968B (en) * | 2014-03-24 | 2016-05-11 | 李永锋 | In a kind of tellurium diethyl dithiocarbamate waste material, reclaim the method for tellurium |
| CN107473189A (en) * | 2017-09-30 | 2017-12-15 | 合肥师范学院 | The preparation method of sea urchin shape nanometer lead telluride and the sea urchin shape nanometer lead telluride being prepared |
| CN107473189B (en) * | 2017-09-30 | 2019-11-26 | 合肥师范学院 | The preparation method of sea urchin shape nanometer lead telluride and the sea urchin shape nanometer lead telluride being prepared |
| CN108217611A (en) * | 2017-12-29 | 2018-06-29 | 北京航空航天大学 | A kind of preparation method of high natrium doping lead telluride |
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Open date: 20091216 |