CN1142099C - Ultrasonic-chemical synthesis process for preparing nm-class metallothio-family compound or phosphide - Google Patents
Ultrasonic-chemical synthesis process for preparing nm-class metallothio-family compound or phosphide Download PDFInfo
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- CN1142099C CN1142099C CNB001265067A CN00126506A CN1142099C CN 1142099 C CN1142099 C CN 1142099C CN B001265067 A CNB001265067 A CN B001265067A CN 00126506 A CN00126506 A CN 00126506A CN 1142099 C CN1142099 C CN 1142099C
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Abstract
The present invention relates to an ultrasonic chemical synthesis preparation method of nanometer sulfide, selenide, telluride or phosphide. The present invention is formed by that ultrasonic radiation reactions are carried out to metal halides or nitrate and elemental sulfur, selenium, tellurium or phosphorus in an organic solvent system under the condition of sealing room temperature, and then products are washed and dried. The method has the advantages of simple technology, mild condition, controllable phases and metering of the products, narrow particle size distribution range of the products, uniform particle shape, good degree of crystallinity, and high productive rate, and the average particle size is smaller than 100 nm. The present invention is suitable for mass production.
Description
Technical field:
The present invention relates to the technology of preparing of sulfide, selenide and the telluride nano powder of the preparation method of nano metal chalcogen compound, particularly copper, silver, lead.
Background technology:
The nano metal chalcogen compound is having a wide range of applications aspect solar cell, light-filter, super ionic material and the semiconductor material, and the research of its preparation method and material character has become one of focus.
According to U.S.'s " solid state chemistry " magazine (J.Solid State Chem., nineteen eighty-three, the 48th volume, the 431st page) and " modern chemistry " (Modern Chemistry, Holt.Reinhart, Winston, New York, nineteen eighty-two, the 54th page) report, chalcogen compound mainly adopts high temperature solid state reaction to prepare, this method needs to carry out under the particular atmosphere protection, and the product particle is big, and its product is easy and by product at high temperature forms sintering, be difficult to obtain the higher product of purity, be unsuitable for lot production; The particularly preparation of selenide and telluride will be a reactant with Selenium hydride or telluretted hydrogen, is severe toxicity, and extremely unstable, introduces impurity easily in product, and is very strict to processing requirement, is difficult to satisfy suitability for industrialized production.
Sonochemistry mainly is to utilize the ultrasonic cavitation process, for chemical reaction provides a kind of new form of energy.The ultrasonic cavitation bubble produces (be liquid drawn back and form the hole), their collapses immediately under consequent sound wave malleation acts on mutually again under the sound wave negative pressure acts on mutually under the sound wave negative pressure acts on mutually.U.S.'s " science " is (nineteen ninety (Science), the 247th volume, the 1067-1069 page or leaf) report, when cavitation bubble collapses, can produce the high temperature of a hundreds of atmospheric high pressure and several thousand degree at its regional area, this provides a kind of extremely special microphysics chemical environment for chemical reaction, and its macro environment approaches normal temperature and pressure." Materials science yearbook " (Annu.Rev.Matl.Sci., 1999, the 29th volume, the 295-326 page or leaf) summary shows, the sonochemical method of nano material is synthetic at present mainly is to carry out in homogeneous system, thereby the product of gained is non-crystal class nano material, and the precursor carbonyl metal compound that is adopted has huge poison and volatile, is difficult to realize suitability for industrialized production.Up to the present, do not see the report that adopts sonochemical method synthetic chalcogen compound, particularly selenide and telluride as yet.
Summary of the invention:
The objective of the invention is to propose a kind of method that adopts sonochemical method at room temperature to prepare nanometer sulfide, selenide or telluride, to overcome the above-mentioned shortcoming that existing preparation method exists.
The sonochemistry synthesis preparation method of metal chalcogen compound of the present invention, be characterised in that at least a metal-salt is dissolved in the amine solvent, add elemental sulfur, selenium or tellurium, after the solution deoxygenation, in the reaction vessel of sealing, under room temperature, carry out the ultrasonic radiation reaction, carry out product washing and dry at last; Described metal-salt comprises halogenide, nitrate, vitriol or the acetate of copper, silver, lead.
The selection of appropriate solvent is one of key of success of the present invention.When preparation sulfide, selenide and telluride, amine solvent can be selected for use,, the carrying out that reacts can be promoted effectively because it has stronger coordination ability and alkalescence, and can play the effect that limits particle growth, thereby form the nanometer product that particle size distribution range is narrow, particle size is little.When preparation tellurium copper, in pure quadrol system, can obtain Cu
4Te
3And when adding a spot of hydrazine hydrate, then obtain Cu
7Te
4When the preparation silver telluride, in pure quadrol system, can obtain Ag
2Te; In ethanol system, then obtain Ag
7Te
4So the present invention can also pass through choice of Solvent, the thing phase of control final product and metering ratio.
The size of product is relevant with the time of the composition of reactant, concentration, solvent types, hyperacoustic intensity and reaction.Usually reactant concn is big more, the reaction times is long more, ultrasonic intensity is low more, and then the product particle diameter is big more.The ultrasonic intensity that adopts should be selected according to reaction system: when the preparation selenide, can adopt frequency is 18KHz, and power is 0.1W/cm
2Common ultrasonic cleaning machine reaction 5-8 hour, be advisable in 6 hours; Also can adopt frequency is 20KHz, and power is 100W/cm
2High-strength ultrasonic 2-4 hour; When the preparation telluride, must adopt frequency is 20KHz, and power is 100W/cm
2High-strength ultrasonic 2-4 hour, be advisable in 3 hours; So both can guarantee to react and carry out relatively fully, can prevent again that the product particle diameter of gained was too big.The temperature of reaction system can be controlled in 25 ± 5 ℃ of room temperature range by recirculated water.
Reactor of the present invention can adopt common ground flask or stainless steel cauldron.When carrying out in common ultrasonic cleaning machine, can select common ground flask for use is reactor; High-strength when ultrasonic when carrying out, adopt stainless reactor better.
Compared with prior art, adopt the inventive method to prepare nanometer sulfide, selenide and telluride, have the following advantages:
Because the present invention adopts in organic solvent system by ultrasonic radiation, can realization response under near room temperature and non-pressurized condition, the products therefrom particle diameter is less, generally at 10-60nm, maximum is no more than 100nm, has avoided the difficult problem that must adopt hot conditions, product particle further to grow up with additive method; And because the dissemination of ultrasonic wave itself makes that the particle size distribution range of products therefrom is narrow, granular size is more even.
The present invention adopts common metal-salt and simple substance, direct reaction in organic solvent and obtain nanometer sulfide, selenide and telluride, avoided prior art to use expensive, hypertoxic, as to be difficult to synthetic organometallics precursor shortcoming, raw material is cheap, be easy to get, and it is relatively stable to air, thereby preparation technology is simple, is easy to amplify and produces in batches, and cost is lower.
The inventive method is because by product can be removed by washing, and product purity is higher.
Adopt the inventive method can also pass through choice of Solvent, the thing phase of control final product and metering ratio.
Because being reflected in the nonhomogeneous system of the inventive method carry out, thereby prepared product all has fine or degree of crystallinity preferably, this be the existing sonochemical method that adopts homogeneous system can't obtain.
Embodiment:
Below in conjunction with embodiment the present invention is done more specifically detailed explanation.
Embodiment 1. preparation Nano lead sulfides
In the 50ml Erlenmeyer flask, hold the 40ml quadrol in advance, add the 1.352g lead chloride and the 0.163g sulphur powder of reaction metering ratio again, Erlenmeyer flask is partly immersed in the water of common ultrasonic cleaning machine of 250W, with 18KHz ultrasonic radiation 4 hours; Products therefrom is washed 2 times through dehydrated alcohol earlier, with distillation washing 2 times, places vacuum drying oven again, 60 ℃ of dryings 4 hours, promptly obtains the Nano lead sulfide powder.
Adopt the analyses of transmission electron microscope (TEM) and ray powder diffraction (XRD) to show that the median size of product lead selenide powder is 70nm, particle is spherical, and product degree of crystallinity is fine.The productive rate that this method prepares the lead sulfide powder reaches 90%.Photoelectron spectrum (XPS) analytical results shows, does not contain the plumbous and chlorine element impurity of simple substance in the product.
If change lead chloride into Silver Nitrate and cupric chloride respectively, can under condition similar to the above, react, make silver sulfide and cupric sulfide respectively.
Embodiment 2. preparation nano lead-selenides
In the 50ml Erlenmeyer flask, hold the 40ml quadrol in advance, add the 1.352g lead chloride and the 0.393g selenium powder of reaction metering ratio again, Erlenmeyer flask is partly immersed 220v, in the water of the common ultrasonic cleaning machine of 250W, ultrasonic radiation is 6 hours under 18KHz; Products therefrom is washed 2 times through dehydrated alcohol earlier, with distillation washing 2 times, places vacuum drying oven again, 60 ℃ of dryings 4 hours, promptly obtains the nano lead-selenide powder.
Adopt the analyses of transmission electron microscope (TEM) and ray powder diffraction (XRD) to show that the median size of product lead selenide powder is 50nm, particle is spherical, and product degree of crystallinity is fine.The productive rate that this method prepares the lead selenide powder reaches 95%.Photoelectron spectrum (XPS) analytical results shows, does not contain simple substance selenium, simple substance lead and chlorine element impurity in the product.
If change lead chloride into Silver Nitrate and cupric chloride respectively, can under condition similar to the above, react, make silver selenide and copper selenide respectively.
Embodiment 3. preparation nano tellurium copper (Cu
4Te
3And Cu
7Te
4)
In the 100ml stainless steel cauldron, hold the 80ml quadrol in advance, add the 0.532g cupric chloride and the 0.3g tellurium powder of reaction metering ratio again, this reactor is designed to guarantee that ultrasound probe immerses 10mm in the solution.Reactor being sealed in guaranteeing that solution temperature is under 25 ± 5 ℃ the condition, is 20KHz with the frequency, and power is 100W/cm
2Ultrasonic radiation 3 hours, products therefrom are washed 2 times through dehydrated alcohol earlier, with distillation washing 2 times, place vacuum drying oven again, 60 ℃ of dryings 4 hours, promptly obtain nanometer Cu
4Te
3Powder.
Adopt the analyses of transmission electron microscope (TEM) and ray powder diffraction (XRD) to show that product tellurium copper powder is the flake nano particle of 30 * 80nm, product degree of crystallinity is better.The productive rate that this method prepares the tellurium copper powder reaches 95%.Photoelectron spectrum (XPS) analytical results shows, does not contain simple substance tellurium, elemental copper and chlorine element impurity in the product.
If in above-mentioned reaction solvent, add a spot of (for example 8ml) hydrazine hydrate, then can under condition similar to the above, react and make the spherical Cu that particle diameter is 12nm
7Te
4Particle.
Embodiment 4. preparation nanometer silver telluride (Ag
2Te and Ag
7Te
4)
In the 100ml stainless steel cauldron, hold the 80ml quadrol in advance, add the 0.795g Silver Nitrate and the 0.3g tellurium powder of reaction metering ratio again, this reactor is designed to guarantee that ultrasound probe immerses 10mm in the solution.Reactor being sealed in guaranteeing that solution temperature is under 25 ± 5 ℃ the condition, is 20KHz with the frequency, and power is 100W/cm
2Ultrasonic radiation 3 hours, products therefrom are washed 2 times through dehydrated alcohol earlier, with distillation washing 2 times, place vacuum drying oven again, 60 ℃ of dryings 4 hours, promptly obtain nanometer Ag
2The Te powder.
Adopt the analyses of transmission electron microscope (TEM) and ray powder diffraction (XRD) to show that product silver telluride powder is the ball shaped nano particle of 20nm, product degree of crystallinity is better.The productive rate that this method prepares the silver telluride powder reaches 85%.Photoelectron spectrum (XPS) analytical results shows, impurity such as oxygen-free tellurium and chlorine element in the product.
If change the solvent in the above-mentioned reaction into ethanol, then can under condition similar to the above, react and make the Ag that particle diameter is 60nm
7Te
4Powder.
Claims (3)
1, a kind of sonochemistry synthesis preparation method of nano metal chalcogen compound, it is characterized in that, at least a metal-salt is dissolved in the amine solvent, add elemental sulfur, selenium or tellurium, after the solution deoxygenation, in the reaction vessel of sealing, under room temperature, carry out the ultrasonic radiation reaction, carry out product washing and dry at last; Described metal-salt comprises halogenide, nitrate, vitriol or the acetate of copper, silver, lead.
2, the sonochemistry synthesis preparation method of nano metal chalcogen compound according to claim 1 is characterised in that, when the preparation selenide, the employing frequency is 18KHz, and power is 0.1W/cm
2Common ultrasonic cleaning machine reaction 6 hours.
3, the sonochemistry synthesis preparation method of nano metal chalcogen compound according to claim 1 is characterised in that, when the preparation telluride, adopting stainless reactor and frequency is 20KHz, and power is 100W/cm
2High-strength ultrasonic 3 hours.
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| CNB001265067A CN1142099C (en) | 2000-08-29 | 2000-08-29 | Ultrasonic-chemical synthesis process for preparing nm-class metallothio-family compound or phosphide |
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| CNB001265067A CN1142099C (en) | 2000-08-29 | 2000-08-29 | Ultrasonic-chemical synthesis process for preparing nm-class metallothio-family compound or phosphide |
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| CN1142099C true CN1142099C (en) | 2004-03-17 |
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Families Citing this family (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1753827B1 (en) * | 2004-05-04 | 2011-10-12 | Centrum für Angewandte Nanotechnologie (CAN) GmbH | Process for preparing dispersible sulfate, preferably barium sulfate nanoparticles |
| CN100374230C (en) * | 2004-11-04 | 2008-03-12 | 宁波大学 | Method for preparing monodisperse granule nano-nickel collosol by strong pulsation ultrasonic wave |
| CN100441509C (en) * | 2005-12-20 | 2008-12-10 | 中国科学院兰州化学物理研究所 | Preparing process of nano copper sulfate particle |
| CN100384741C (en) * | 2006-08-24 | 2008-04-30 | 同济大学 | Method of preparing sulfide nano material of lead with calixarene adjusting solvent thermal system |
| KR101030780B1 (en) * | 2007-11-14 | 2011-04-27 | 성균관대학교산학협력단 | Synthesis of i-iii-vi2 nanoparticles and fabrication of polycrystalline absorber layers |
| CN101328607B (en) * | 2008-04-23 | 2011-02-09 | 武汉理工大学 | Preparation of Zn2P3 nanorod |
| CN101935024B (en) * | 2010-09-09 | 2012-01-11 | 哈尔滨工业大学 | Method for preparing Cu7Te4 nano-belt semiconductor material |
| CN102060273A (en) * | 2010-11-05 | 2011-05-18 | 桂林理工大学 | Method for preparing I-III-VI group semiconductor material through solvothermal synthesis in constant pressure open system |
| CN102515842B (en) * | 2011-11-23 | 2013-08-07 | 陕西科技大学 | Method for preparing cobalt sulfide nano film by ultrasonic chemical method |
| CN103372652A (en) * | 2012-04-16 | 2013-10-30 | 合肥杰事杰新材料股份有限公司 | Method for using ultrasound irradiation to prepare nano Ag/PVP (Ag/ polyvinyl pyrrolidone) composite |
| FR3008705A1 (en) * | 2013-07-18 | 2015-01-23 | Meto & Co | COMPOSITE COATINGS OF COPPER OXIDE AND / OR PHOSPHORUS |
| US20180162732A1 (en) * | 2015-06-01 | 2018-06-14 | Baoshan Iron & Steel Co., Ltd. | Method of preparing metal chalcogenide nanomaterials |
| CN111019152B (en) * | 2019-12-17 | 2021-04-09 | 浙江大学 | Method for ultrasonic-assisted synthesis of zirconium-based metal organic framework material and product thereof |
| CN114477113B (en) * | 2021-12-15 | 2023-04-18 | 中国科学院深圳先进技术研究院 | Preparation and application of two-dimensional cuprous phosphide/bismuth selenide heterojunction composite material |
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