CN1251348A - Method for preparing nanometer material of compound of sulfur family and phosphorus family - Google Patents
Method for preparing nanometer material of compound of sulfur family and phosphorus family Download PDFInfo
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- CN1251348A CN1251348A CN 98119471 CN98119471A CN1251348A CN 1251348 A CN1251348 A CN 1251348A CN 98119471 CN98119471 CN 98119471 CN 98119471 A CN98119471 A CN 98119471A CN 1251348 A CN1251348 A CN 1251348A
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Abstract
The preparation method of chalcogenide or phosphorus family compound nanometer material is characterized by that mixing the metal salt, chalcogen or phosphorus family non-metallic elementary substance and hydroborates metered according to its chemical reaction equation in organic solvent, completely reacting, filtering, washing and drying to obtain the invented produt. Said invention is implemented at room-temp., simple in operation and easy to implement, its raw material is cheap and easily available, it can save energy source, reduce cost,and is safe in operation and applicable to large-scale production of chalcogen and phosphorus family semiconductive material.
Description
The invention relates to the technical field of chemical reduction preparation methods of semiconductor nano materials, in particular to a preparation technology of selenide, phosphide, sulfide, arsenide, antimonide and telluride nano materials.
The semiconductor nano material has wide application prospect in the aspects of nonlinear optical devices, photoelectric devices, solar cells and the like. Journal of the material science (j. mater.sci., 1990, 25, 1159) and the chemical society of review (chem.soc.rev, 1996, 25, 199) in the united kingdom have reported the preparation of semiconductor materials using high temperature self-propagating reaction methods and solid phase metathesis methods, respectively, but both require high temperatures; although the method reported by "journal of chemical society, dalton journal" (j.chem.soc., dalton. trans., 1997, 231. one. 236) of royal kingdom is a room temperature reaction, the reaction needs to be carried out in liquid ammonia which is easy to explode, and the operation of the reaction in the liquid ammonia is complicated, and the obtained product has a large size, and some of the products are amorphous. At present, the chalcogen phosphorus family nanometer material is prepared by pyrolyzing metal organic precursors, but the method needs complicated and expensive instruments and equipment, and the preparation of the precursors is difficult. Borohydride has been reported as a reducing agent for preparing metal simple substances in journal of Science (Science, vol.246, 1260, 1989), but borohydride has not been reported for preparing semiconductor nanomaterials.
The invention aims to provide a method for preparing a chalcogenide or phosphorus compound nano material by borohydride reduction.
The preparation method of the nanometer material of the sulfur group or phosphorus group compound is characterized in that the metal salt MX metered according to the chemical reaction equationnMixing the nonmetal simple substance E and borohydride in an organic solvent, reacting completely, filtering, washing and drying; wherein M is Cu, Ag, Zn, Cd, Hg, Fe, Co, Ni, Ge, Sn, Pb, Al, Ga, In, As, Sb or Bi; x is F-、Cl-、Br-、I-、NO3 -Or SO4 2-(ii) a n is the value of the valence of the corresponding M metal ion divided by the number of charges of the corresponding anion X; e is S, Se, Te, P, As or Sb; the borohydride is derived from LiBH4、NaBH4Or KBH4Selecting; the organic solvent is selected from benzene, toluene, ethylenediamine, polyamine, pyridine, carbon disulfide, tetrahydrofuran, alcohols or ethers.
The reaction of the process of the invention can be carried out at room temperature to 200 ℃; the most important advantage is that these reactions can be carried out at room temperature and normal pressure.
Because the method of the invention dissolves metal salt and sulfur family or phosphorus family simple substance in organic solvent for reaction, compared with solid phase reaction method, the contact chance between reactants is greatly increased, and the reduction action of borohydride is added, so that the metal salt can react with the sulfur family and phosphorus family simple substance at room temperature and normal pressure, and the solvent can absorb the heat generated in the reaction process, so that the reaction can be carried out smoothly; and the solvent has the function of dissolution or complexation, so that the corresponding nano semiconductor material can be obtained.
Because the raw material MX used in the methodnThe anion X in the method does not actually participate in the reaction, so the selection range of the anion in the raw material is wider, and the method is suitable for wide selection range of the raw material; due to the organic solventThe method has the functions of dissolving or complexing, and different solvents can be selected aiming at different metal salts and sulfur group and phosphorus group simple substances to facilitate the reaction; according to the similarity of chemical properties of the same group elements of Cu, Ag, Zn, Cd, Hg, Fe, Co, Ni, Ge, Sn, Pb, Al, Ga, In, As, Sb and Bi and S, Se, Te, P, As and Sb, a series of corresponding chalcogenide or phosphorus semiconductor nano materials can be prepared by the method, so that the application range of the method is wider.
The reduction preparation method adopted by the invention can be carried out at room temperature and normal pressure, the operation is simple and easy, the raw materials are cheap and easy to obtain, the defects that high-temperature equipment and complex and expensive instruments and equipment are required to be used in the existing method are avoided, and the danger of explosion caused by using liquidammonia is avoided; the method can save energy, reduce cost and has safe operation; the method is suitable for large-scale production of chalcogenide and phosphorus semiconductor materials.
The following are examples of the present invention.
Example 1. preparation of nano silver selenide material at room temperature:
reaction formula is
Selecting a glass bottle with a ground stopper and a capacity of 100mL, firstly filling 20mL of ethylenediamine into the bottle, and then weighing 0.85 g of AgNO by using a balance30.40 g selenium powder and 0.20 g KBH4Putting the mixture into a bottle, tightly plugging the ground stopper, and quickly generating black precipitates in the solution; standing at room temperature for about 4 hours until colorless AgNO3The crystals completely disappeared and no black precipitate increased, the ground bottle was opened, the resulting precipitate was filtered, washed with water and air dried naturally at room temperature to obtain 0.66 g of product. The obtained product is determined to be pure Ag by X-ray powder diffraction method2Se; the particles were observed by an electron microscope to be spherical particles having a particle diameter of 15. + -.2 nm.
With CuCl2In place of the above AgNO3By the same method as above, Cu can be obtained2Se nano material, Cu of sheet shape characterized by transmission electron microscope2Se nano material.
Example 2 preparation of nano cadmium selenide material at room temperature:
reaction formula is
Selecting a glass bottle with a ground stopper and a capacity of 100mL, firstly filling 20mL of ethylenediamine into the bottle, and then weighing 0.90 g of CdCl20.40 g selenium powder and 0.20 g KBH4Placing into a bottle, plugging the ground stopper, allowing black precipitate to appear in the solution quickly, standing at room temperature for 4 hr, and collecting white granular CdCl2The starting material disappeared completely and the black precipitate did not increase any more, the ground bottle was opened and the precipitate was filtered, washed with water and dried naturally at room temperature to obtain 0.83 g of product. The obtained product was measured by X-ray powder diffraction method and was determined to bePure CdSe; the average particle size can be calculated to be 10nm from the broadening of diffraction peaks according to the Sherle formula; the product is observed by an electron microscope, and is known as particles with the particle size of 10 +/-3 nm, and the shape of the particles is rod-shaped.
Respectively with ZnCl2、NiCl2、PbCl2And SnCl2In place of the above-mentioned CdCl2The ZnSe, NiSe, PbSe and SnSe nano materials can be respectively prepared by adopting the same method.
Example 3 room temperature preparation of nano bismuth selenide material:
reaction formula is
Selecting a glass bottle with a ground stopper and a capacity of 100mL, firstly filling 20mL of ethylenediamine into the bottle, and then weighing 1.6 g of BiCl30.6 g selenium powder and 0.8 g KBH4Placing into a bottle, plugging the ground stopper, allowing black precipitate to appear in the solution quickly, standing at room temperature for 4 hr, and collecting white powder BiCl3The starting material disappeared completely and the black precipitate did not increase anymore, the ground bottle was opened and the precipitate obtained was filtered, washed with water and dried naturally at room temperature to obtain 1.6 g of product. The obtained product was measured by X-ray powder diffraction method to determine pure Bi2Se3(ii) a The average particle size can be calculated from the broadening of diffraction peaks according to the Sherle formula to be 20 nm; the product is observed by an electron microscope, and the particle size is 20 +/-3 nm, and the shape of the particle is rod-shaped.
Respectively with AsCl3And SbCl3In place of the above BiCl3As obtained by the same method As above2Se3And Sb2Se3And (3) nano materials.
Example 4 preparation of nano indium phosphide material at room temperature:
reaction formula is
Selecting a glass bottle with a ground opening and a capacity of 100mL, filling 20mL of absolute ethyl alcohol into the bottle, and weighing 1.10 g of InCl30.20 g of white phosphorus and 0.1 g of KBH4Putting the mixture into a bottle, tightly plugging the ground stopper, and allowing black precipitates to appear in the solution after about 10 minutes; after standing at room temperature for 12 hours, the black precipitate does not increase any more, the ground bottle is opened, the obtained precipitate is filtered, washed with dilute hydrochloric acid with the concentration of 0.5mol/L, washed with distilled water and naturally dried at room temperature to obtain 0.50 g of product. Determining the InP as pure InP by X-ray powder diffraction method; according to the scherrer equation, the average particle size was 15nm as calculated from the broadening of the diffraction peak.
With NiCl2Instead of InCl3Ni having an average particle diameter of 20nm can be obtained in the same manner as described above2P。
Claims (1)
1. A process for preparing the nano material of sulfur family or phosphorus family features that the metal salt MX is proportionally prepared from the metal salt MXnMixing the nonmetal simple substance E and borohydride in an organic solvent, reacting completely, filtering, washing and drying; wherein M is Cu, Ag, Zn, Cd, Hg, Fe, Co, Ni, Ge, Sn, Pb, Al, Ga, In, As, Sb or Bi; x is F-、Cl-、Br-、I-、NO3 -Or SO4 2-(ii) a n is the value of the valence of the corresponding M metal ion divided by the number of charges of the corresponding anion X; e is S, Se, Te, P, As or Sb; the borohydride is derived from LiBH4、NaBH4Or KBH4Selecting; the organic solvent is selected from benzene, toluene, ethylenediamine,Polyamine, pyridine, carbon disulfide, tetrahydrofuran, alcohols or ethers.
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CN 98119471 CN1086177C (en) | 1998-10-15 | 1998-10-15 | Method for preparing nanometer material of compound of sulfur family and phosphorus family |
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CN 98119471 CN1086177C (en) | 1998-10-15 | 1998-10-15 | Method for preparing nanometer material of compound of sulfur family and phosphorus family |
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Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2004073021A3 (en) * | 2003-01-31 | 2005-01-13 | Univ Arizona | Preparation of metal chalcogenides from reactions of metal compounds and chalcogen |
CN101328607B (en) * | 2008-04-23 | 2011-02-09 | 武汉理工大学 | Preparation of Zn2P3 nanorod |
CN107934923A (en) * | 2017-11-07 | 2018-04-20 | 陕西科技大学 | A kind of nanometer sheet self assembly flower ball-shaped Sb2Se3The preparation method of anode material of lithium-ion battery |
CN107946559A (en) * | 2017-11-07 | 2018-04-20 | 陕西科技大学 | A kind of solvent hot preparation sodium-ion battery anode Sb2Se3The method of/C composite |
-
1998
- 1998-10-15 CN CN 98119471 patent/CN1086177C/en not_active Expired - Fee Related
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2004073021A3 (en) * | 2003-01-31 | 2005-01-13 | Univ Arizona | Preparation of metal chalcogenides from reactions of metal compounds and chalcogen |
CN101328607B (en) * | 2008-04-23 | 2011-02-09 | 武汉理工大学 | Preparation of Zn2P3 nanorod |
CN107934923A (en) * | 2017-11-07 | 2018-04-20 | 陕西科技大学 | A kind of nanometer sheet self assembly flower ball-shaped Sb2Se3The preparation method of anode material of lithium-ion battery |
CN107946559A (en) * | 2017-11-07 | 2018-04-20 | 陕西科技大学 | A kind of solvent hot preparation sodium-ion battery anode Sb2Se3The method of/C composite |
CN107946559B (en) * | 2017-11-07 | 2020-04-10 | 陕西科技大学 | Sb for solvothermal preparation of sodium ion battery cathode2Se3Method for preparing/C composite material |
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CN1086177C (en) | 2002-06-12 |
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