CN100595160C - Method for preparing tin oxide nanocrystalline coated by organic ligand - Google Patents
Method for preparing tin oxide nanocrystalline coated by organic ligand Download PDFInfo
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- CN100595160C CN100595160C CN200710193594A CN200710193594A CN100595160C CN 100595160 C CN100595160 C CN 100595160C CN 200710193594 A CN200710193594 A CN 200710193594A CN 200710193594 A CN200710193594 A CN 200710193594A CN 100595160 C CN100595160 C CN 100595160C
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Abstract
The invention provides a synthesis method of tin oxide nano-crystal which is wrapped by organic ligands. The method is that: tin source and organic wrapping agent are added into toluene; the mixture is heated, dissolved and added with water solution of alkaline matter, then sent into a reaction vessel at the temperature of 120-180 DEG C to react for 1-24 hours; the tine source is hydrolyzed; afternucleation and growing process, the tin oxide nano-crystal wrapped with organic ligands is prepared. The whole preparation method of the invention is characterized in that reaction condition is moderate, the operation is simple and the preparation period is short, thereby the preparation method can be easily put into mass production. In addition, the tin oxide nano-crystal with different sizes and shapes such as spherical shape and branch shape can be prepared by adjusting reaction time, temperature, alkaline amount, water amount and organic wrapping agent type; the size and shape of the synthesized tin oxide nano-crystal can also be controlled; the size distribution is narrow, and the nano-crystal can be dissolved into organic solvent with different heteropolarities through surface ligand exchange.
Description
Technical field
The invention belongs to the stannic oxide (SnO that organic ligand coats
2) preparation of nano crystal, be specifically related to utilize two phase process to prepare the preparation method of stannum oxide nano-crystal in conjunction with autoclave.
Background technology
Tindioxide is that (Eg=3.5eV 300K), can be used as uses such as gas sensitive, humidity-sensitive material, pressure sensitive and photochromics for a kind of n N-type semiconductorN of broad-band gap.At aspects such as gas sensor, catalyzer, lithium-ion secondary cell, fuel cell, solar cell and field-effect transistors important use is arranged.Recent two decades comes, and along with the development of nano science and technology, nano tin dioxide synthetic also carried out gradually and show wide application prospect (Penny, M.W.et.al., Charge storage in SnO
2Nanoparticles:A method andmechanism for charge writing/erasing, Applied Physics Letters, 2007 (91), 16).Up to the present, can adopt several different methods to prepare stannic oxide nano material, vacuum-evaporation gel method for example, elevated temperature heat decomposition method, Metalorganic chemical vapor deposition method and to adopt high-purity Sn powder be raw material, high temperature is synthetic under the water subsidiary conditions.The starting material that aforesaid method adopted are expensive, the method and apparatus complexity, and temperature of reaction is higher, about more than 500 ℃, is unfavorable for realizing that certain scale prepares stannic oxide nano material.
Summary of the invention
Temperature of reaction height, restive nanocrystalline size and dimension and the nanocrystalline shortcoming that is difficult to be dispersed in the organic solvent of institute's synthetic when synthesizing in order to solve tradition.The invention provides a kind of preparation method of stannum oxide nano-crystal of organic ligand coating, that is: the hot method of two-phase.It is under the reaction conditions of gentleness, utilizes the preparation method of the narrower stannum oxide nano-crystal of two-phase interface preparation size and controllable shapes and distribution of sizes.
Secondly, by the surface ligand exchange, nanocrystalline the dissolving in the different organic solvent of polarity of the hot method preparation of two-phase.This has solved the difficult problem of stannum oxide nano-crystal in application.Therefore, the hot method of two-phase institute synthetic size, controllable shapes, the stannum oxide nano-crystal that can be dissolved in the organic solvent can be widely used.
The present invention utilizes the advantage of two-phase synthetic method, with the stannic acid tert-butyl ester as Xi Yuan, with the aqueous solution of TERTIARY BUTYL AMINE, n-Butyl Amine 99, urea, sodium-acetate at a certain temperature, in autoclave, react, by organic coating agent, coat as oleyl amine, oleic acid or TETRADECONIC ACID.The stannum oxide nano-crystal that generates can stably be dispersed in the non-polar solvent as toluene.The stannum oxide nano-crystal that carries out obtaining after the ligand exchange with pyridine can stably be dispersed in the polar solvent as methyl alcohol, pyridine.Overcome traditional temperature of reaction height, restive nanocrystalline size and dimension and nanocrystalline shortcoming that is difficult to be dispersed in the organic solvent of institute's synthetic when synthetic.
The preparation method of the stannum oxide nano-crystal that a kind of organic ligand provided by the invention coats has following two:
The step of first method of the present invention and condition are:
The Xi Yuan that adopts is the stannic acid tert-butyl ester;
The organic coating that adopts is: oleyl amine, oleic acid or TETRADECONIC ACID;
Alkaline matter is: TERTIARY BUTYL AMINE, n-Butyl Amine 99, urea or sodium-acetate;
According to raw-material proportioning, the stannic acid tert-butyl ester and organic coating joined in the toluene dissolve, the mol ratio of organic coating and Xi Yuan is 90: 1～15: 1, the concentration range of Xi Yuan in toluene solution is 0.002mol/L～0.04mol/L, the aqueous solution that adds alkaline matter then, aqueous solution neutral and alkali material concentration scope is 0.1mol/L～0.25mol/L, keeping the mol ratio of alkaline substance and Xi Yuan is 150: 1～1: 4, under 120 ℃ of conditions, react 1h-24h, be reflected in the autoclave and carry out, pressure is at 1MPa-10MPa, and the hydrolysis of tin source obtains the stannum oxide nano-crystal that organic ligand coats.
Stannum oxide nano-crystal can be dissolved in non-polar solvent such as the toluene.Its X-ray diffractogram as shown in Figure 1.Its transmission electron microscope as shown in Figure 2.
The step of second method of the present invention and condition are:
The stannum oxide nano-crystal that the organic ligand that first above-mentioned method of the present invention is obtained coats, be dispersed in non-polar organic solvent toluene or the trichloromethane, the nanocrystalline pyridine that is dissolved in that above-mentioned oil phase centrifugation is obtained, nanocrystalline concentration range is 0.00001mol/L～0.001mol/L in the maintenance pyridine, at 60 ℃ of reflux 6h, obtain the stannum oxide nano-crystal that pyridine coats.
Stannum oxide nano-crystal can be dissolved in polar solvent such as methyl alcohol or the pyridine.
This is nanocrystalline can be dissolved in polar organic solvent, for example methyl alcohol or pyridine.
The type of the amount by adjusting reaction time, temperature of reaction, alkali, the amount of water and organic coating can synthesize different size spherical, the branch shape is nanocrystalline.Institute's synthetic stannum oxide nano-crystal size and dimension is all controlled, and distribution of sizes is narrower, and by surface ligand exchange, nanocrystalline dissolving in the different organic solvent of polarity.
Beneficial effect: the method that the present invention prepares stannum oxide nano-crystal has gentleness of reaction conditions, the characteristics that method is simple, and preparation cycle is short, thereby be easy to amplification test.By ligand exchange, prepared stannum oxide nano-crystal can be dispersed in the organic solvent of opposed polarity.The type of the amount by adjusting reaction time, temperature of reaction, alkali, the amount of water and organic coating can be synthesized the stannum oxide nano-crystal that the organic ligand spherical, the branch shape of different size coats.And by surface ligand exchange, nanocrystalline dissolving in the different organic solvent of polarity.
Description of drawings
The X ray diffracting spectrum of the stannum oxide nano-crystal that Fig. 1 organic ligand coats.
Fig. 2 is the transmission electron microscope picture of the stannum oxide nano-crystal of organic ligand coating.
Embodiment
Embodiment 1: the preparation of the stannum oxide nano-crystal that the spherical organic part coats:
0.15mmol Xi Yuan, 0.5g TETRADECONIC ACID and 25ml toluene are joined the teflon lined of the autoclave of 30ml, the aqueous solution that again 2ml is contained the 0.2ml n-Butyl Amine 99 adds system, after autoclave sealed, put into the inherent 120 ℃ of heating 1h (pressure remains on 1-10MPa) of stove, the cooling back is in the nanocrystalline generation of oil phase adularescent.Its particle diameter is about 2nm.Can be dispersed in non-polar organic solvent such as toluene or the trichloromethane.The centrifugal nanocrystalline precipitation that obtains of above-mentioned oil phase is dissolved in the 15ml pyridine,, obtains the stannum oxide nano-crystal that pyridine coats at 60 ℃ of reflux 6h.
Embodiment 2: the preparation of the stannum oxide nano-crystal that branch shape organic ligand coats:
0.05mmol Xi Yuan, 1ml oleic acid and 20ml toluene are joined the teflon lined of the autoclave of 30ml, the aqueous solution that again 5ml is contained the 0.5ml TERTIARY BUTYL AMINE adds system, autoclave is sealed and put into the inherent 180 ℃ of heating 12h (pressure remains on 1-10MPa) of stove, the cooling back is in the nanocrystalline generation of oil phase adularescent.This nanocrystalline being dispersed in non-polar organic solvent such as toluene or the trichloromethane.The branch width is approximately 1.5nm.
Embodiment 3: the preparation of the stannum oxide nano-crystal that branch shape organic ligand coats:
0.02mmol Xi Yuan, 0.5g oleyl amine and 10ml toluene are joined in the teflon lined of autoclave of 30ml, the aqueous solution that again 2ml is contained 0.0012g urea adds system, autoclave is sealed and put into the inherent 180 ℃ of heating 6h (pressure remains on 1-10MPa) of stove, the cooling back is in the nanocrystalline generation of oil phase adularescent.It is shaped as the branch shape.The nanocrystalline precipitation that above-mentioned oil phase centrifugation is obtained is dissolved in the 10ml pyridine, at 60 ℃ of reflux 6h, obtains the stannum oxide nano-crystal that pyridine coats.
Embodiment 4: the preparation of the stannum oxide nano-crystal that the spherical organic part coats:
0.4mmol Xi Yuan, 2ml oleic acid and 10ml toluene are joined in the teflon lined of autoclave of 30ml, the aqueous solution that again 5ml is contained the 0.2ml TERTIARY BUTYL AMINE adds system, autoclave is sealed and put into the inherent 150 ℃ of heating 12h (pressure remains on 1-10MPa) of stove, the cooling back is in the nanocrystalline generation of oil phase adularescent.It is shaped as spherical.
Embodiment 5: the preparation of the stannum oxide nano-crystal that the spherical organic part coats
0.1mmol Xi Yuan, 0.5ml oleyl amine and 5ml toluene are joined in the teflon lined of autoclave of 30ml, the aqueous solution that again 5ml is contained 0.006g urea adds system, autoclave is sealed and put into the inherent 140 ℃ of heating 3h (pressure remains on 1-10MPa) of stove, the cooling back is in the nanocrystalline generation of oil phase adularescent.It is shaped as arrow shaped.
Embodiment 6: the preparation of the stannum oxide nano-crystal that the spherical organic part coats
0.3mmol Xi Yuan, 1ml oleic acid and 20ml toluene are joined in the teflon lined of autoclave of 30ml, the aqueous solution that again 1ml is contained the 0.0004g sodium-acetate adds system, autoclave is sealed and put into the inherent 120 ℃ of heating 5h (pressure remains on 1-10MPa) of stove, the cooling back is in the nanocrystalline generation of oil phase adularescent.It is shaped as arrow shaped.
Claims (1)
1. the preparation method of the stannum oxide nano-crystal that coats of organic ligand is characterized in that its step and condition are:
The Xi Yuan that adopts is the stannic acid tert-butyl ester;
The organic coating that adopts is: oleyl amine, oleic acid or TETRADECONIC ACID;
Alkaline matter is: TERTIARY BUTYL AMINE, n-Butyl Amine 99, urea or sodium-acetate;
According to raw-material proportioning, the stannic acid tert-butyl ester and organic coating joined in the toluene dissolve, the mol ratio of organic coating and Xi Yuan is 90: 1～15: 1, the concentration range of Xi Yuan in toluene solution is 0.002mol/L～0.04mol/L, the aqueous solution that adds alkaline matter then, aqueous solution neutral and alkali material concentration scope is 0.1mol/L～0.25mol/L, keeping the mol ratio of alkaline substance and Xi Yuan is 150: 1～1: 4, under 120 ℃ of conditions, react 1h-24h, be reflected in the autoclave and carry out, pressure is at 1MPa-10MPa, and the hydrolysis of tin source obtains the stannum oxide nano-crystal that organic ligand coats;
The stannum oxide nano-crystal of the organic ligand coating that obtains, be dispersed in non-polar organic solvent toluene or the trichloromethane, the nanocrystalline pyridine that is dissolved in that above-mentioned oil phase centrifugation is obtained, nanocrystalline concentration range is 0.00001mol/L～0.001mol/L in the maintenance pyridine, at 60 ℃ of reflux 6h, obtain the stannum oxide nano-crystal that pyridine coats.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102133543B (en) * | 2010-12-23 | 2013-08-21 | 西北师范大学 | Preparation of tin dioxide-carbon nitrogen composite material |
| CN102602985B (en) * | 2012-04-11 | 2013-12-11 | 吉林大学 | Method for preparing nanometer stannous oxide and nanometer stannic oxide |
| CN103556303B (en) * | 2013-10-19 | 2015-06-10 | 山东大学 | Preparation method of tin oxide fiber precursor and tin oxide crystal fibers |
| CN103746099B (en) * | 2014-01-17 | 2015-10-28 | 江苏华盛精化工股份有限公司 | The preparation method of the carbon fibre material of a kind of tin ash parcel, product and application |
| CN110451557A (en) * | 2019-07-25 | 2019-11-15 | 杭州电子科技大学 | A kind of SnO with hierarchical structure2Nano whisker/nano-particles reinforcement cluster and its application |
Citations (3)
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| CN1635032A (en) * | 2004-12-03 | 2005-07-06 | 中国科学院长春应用化学研究所 | Process for synthesizing organic ligand coated titanium dioxide nano particles |
| CN1657418A (en) * | 2004-02-16 | 2005-08-24 | 北京化工大学 | Tin dioxide powder-and its preparation method |
| CN1821086A (en) * | 2005-12-28 | 2006-08-23 | 中国科学院长春应用化学研究所 | Method for synthesizing organic ligand coated zirconium oxide nano crystal |
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Patent Citations (3)
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| CN1657418A (en) * | 2004-02-16 | 2005-08-24 | 北京化工大学 | Tin dioxide powder-and its preparation method |
| CN1635032A (en) * | 2004-12-03 | 2005-07-06 | 中国科学院长春应用化学研究所 | Process for synthesizing organic ligand coated titanium dioxide nano particles |
| CN1821086A (en) * | 2005-12-28 | 2006-08-23 | 中国科学院长春应用化学研究所 | Method for synthesizing organic ligand coated zirconium oxide nano crystal |
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| 氧化铁磁性纳米粒子的制备、表面修饰及在分离和分析中的应用. 赵紫来等.化学进展，第18卷第10期. 2006 * |
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Owner name: CHANGZHOU INSTITUTE OF ENERGY STORAGE MATERIALS + Free format text: FORMER OWNER: CHANGCHUN INST. OF APPLIED CHEMISTRY, CHINESE ACADEMY OF SCIENCES Effective date: 20140930 |
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Effective date of registration: 20140930 Address after: Changzhou City, Jiangsu province Hehai road 213000 No. 9 Patentee after: Changzhou Institute of Energy Storage Materials & Devices Address before: 130022 Changchun people's street, Jilin, No. 5625 Patentee before: Changchun Institue of Applied Chemistry, Chinese Academy of Sciences |