CN103588241B - A kind of preparation method of the three-dimensional stannous sulfide micro-flowers of quaternary ammonium salt auxiliary complex-former synthesis - Google Patents
A kind of preparation method of the three-dimensional stannous sulfide micro-flowers of quaternary ammonium salt auxiliary complex-former synthesis Download PDFInfo
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Abstract
The preparation method that the invention discloses the three-dimensional stannous sulfide micro-flowers of a kind of quaternary ammonium salt auxiliary complex-former synthesis, belongs to technical field of inorganic nano-material preparation; Its step is under agitation to be dissolved in deionized water by a certain percentage to form the settled solution containing thiostannate root complex ion by butter of tin and chelating agent, then under agitation add pattern and structure regulator, sulfur source, this reaction system is transferred in the stainless steel cauldron that liner is politef; It is placed in drying baker, hydro-thermal reaction certain time under uniform temperature, then naturally cools to room temperature, gained precipitate with deionized water and dehydrated alcohol are rinsed respectively, centrifugation, in vacuum drying oven inner drying; Dried sample is placed in tube furnace, calcines under nitrogen protection, stannous sulfide (SnS) micro-flowers can be obtained; It is simple that the synthetic method of the present invention has technique, and cost is low, the advantage that productivity is high, and the stannous sulfide micro-flowers size of synthesis and pattern are comparatively uniform, and average diameter is 5 ��m��18 ��m.
Description
Technical field
The preparation method that the present invention relates to a kind of nano material, the preparation method being specifically related to the three-dimensional stannous sulfide micro-flowers of a kind of quaternary ammonium salt auxiliary complex-former synthesis, belong to technical field of inorganic nano-material preparation.
Background technology
There is the inorganic micro-nano functional material of controlled dimensions and pattern, it is particularly the micro Nano material with three-dimensional hierarchical organization that elementary cell forms by nanostructured, due to its have concurrently nanometer and the advantage of micro-meter scale and there is the optical, electrical performance of novelty, thus causing the great interest of people and concern. Stannous sulfide is the semi-conducting material that a class is important, and its direct band gap is 1.2 ~ 1.5eV, and indirect band gap is 1.0 ~ 1.1eV, has high conversion efficiency, is used to prepare the good material of solar cell device absorbed layer.In addition, outstanding photoelectric property and simple substance S and Sn be widespread in nature and have environment-protecting asepsis evil etc. feature, again show that stannous sulfide photoconduction, near infrared detector, holographic recording system field significant advantage (Du Jinhui etc., optoelectronic laser, 2002,889).
At present, the research of stannous sulfide micro nano structure be concentrated mainly on nano wire (C.H.An etc., JournalofCrystalGrowth, 2003,581; Y.K.Liu etc., ChemicalPhysicsLetters, 2003,67), stannous sulfide micron bar thin film (Du Yuanbao etc., Zhejiang Normal University's journal, 2013,65), fullerene-like nanoparticles (S.Y.Hong etc., TheJournalofAmericanChemistySociety, 2003,10470), nanometer thin plate (D.Chen etc., JournalofCrystalGrowth, 2004,469) nano flower (H.M.Hu etc., being made up of nanometer rods or nanometer sheet, MaterialsChemistyandPhysics, 2004,233; D.D.Vaughn etc., ChemicalCommunications, 2012,5608; J.J.Ning etc., Nanoscale, 2010,1699) etc., quantum dot (C.Prastani etc., MaterialsScienceandEngineeringB, 2013,656), nanocrystalline (D.S.Koktysh etc., MaterialsScienceandEngineeringB, 2010,117) etc. Its preparation method includes hydro-thermal and solvent-thermal method, electrochemical deposition method, laser lift-off, microwave method, the wet-chemical sedimentation method etc. In the method for the micro Nano material with three-dimensional hierarchical organization being wherein made up of stannous sulfide nanometer sheet in preparation, some needs are using organic reagent such as polyhydric alcohol or ethylenediamine as solvent, and reacted waste liquid is easily to environment; What have is then that reactions steps is more and complicated.
In the method, with sodium sulfide for chelating agent, the tin ion of positively charged is changed into electronegative thiostannate radical ion, adopting quaternary ammonium salt tetrabutyl ammonium bromide is pattern and structure regulator, utilize the TBuA radical ion of positively charged and the electrostatic interaction of electronegative thiostannate radical ion, adopt hydro-thermal and heat treatment technics at lower temperature and to synthesize pattern in the short period and size is comparatively uniform, the method for the stannous sulfide micro-flowers with three-dimensional hierarchical organization that is made up of two-dimensional nano sheet yet there are no open report.
Summary of the invention
It is an object of the invention to provide a kind of method synthesizing three-dimensional stannous sulfide micro-flowers, the method can in relatively low temperature with in the shorter time, adopt relatively simple technique and raw material cheap and easy to get, rapid, high volume synthesis dispersibility better, pattern and the comparatively uniform stannous sulfide micro-flowers of size.
For realizing the purpose of foregoing invention, the technical scheme that the present invention takes is as follows:
The preparation method of the three-dimensional stannous sulfide micro-flowers of a kind of quaternary ammonium salt auxiliary complex-former synthesis, comprises the steps:
(1) butter of tin is under agitation dissolved in deionized water and forms settled solution A;
(2) being dissolved in deionized water by chelating agent, obtain solution B, be then added dropwise in solution A by solution B, Mr.'s yellowly precipitates, and continues dropping, eventually forms clear solution C;
(3) under agitation pattern and structure regulator, sulfur source addition solution C will obtain solution D;
(4) the reaction system solution D that step (3) obtains is transferred in the stainless steel cauldron that liner is politef, it is placed in drying baker, react 4 ~ 10 hours under hydrothermal condition, then room temperature is naturally cooled to, gained precipitate with deionized water and dehydrated alcohol are rinsed three times respectively, centrifugation and in vacuum drying oven 50 ~ 70 DEG C dry within 10 ~ 14 hours, obtain product;
(5) being placed in tube furnace by products obtained therefrom, 300 ~ 500 DEG C of heat treatments can obtain three-dimensional stannous sulfide micro-flowers for 2 ~ 4 hours under nitrogen protection;
The molar concentration that addition is tin ion of the butter of tin described in step (1) is 0.007��0.07mol/L;
Chelating agent described in step (2) is sodium sulfide;
The addition of described chelating agent is: the mol ratio of chelating agent and tin ion is 4.0 ~ 6.0:1;
Pattern and structure regulator described in step (3) are quaternary ammonium salt tetrabutyl ammonium bromide;
Described pattern and the addition of structure regulator be: the mol ratio of pattern and structure regulator and tin ion is 1.0 ~ 6.0:1;
Sulfur source described in step (3) is thiourea or thioacetamide;
The addition in described sulfur source is: the mol ratio of sulfur source and tin ion is 4.0 ~ 6.0:1;
Hydrothermal condition described in step (4) is 160 ~ 180 DEG C;
The method regulates the size of stannous sulfide flower-like microsphere by the mol ratio or response time changing tin ion concentration or pattern and structure regulator and tin ion.
The invention has the beneficial effects as follows:
(1) present invention have preparation technology simple, with low cost, can rapid, high volume synthesis and the high advantage of product yield.
(2) the stannous sulfide micro-flowers size prepared and pattern are comparatively uniform, and average diameter is at 5 ��m��18 ��m. This product is expected to obtain in fields such as lithium ion battery electrode material, photocatalyst and solar cell materials be widely applied.
Accompanying drawing explanation
Fig. 1 is the X-ray diffractogram of the stannous sulfide micro-flowers that the present invention prepares;
Fig. 2 is the scanning electron microscope (SEM) photograph of the stannous sulfide micro-flowers that the present invention prepares;
Fig. 3 is the scanning electron microscope (SEM) photograph of the stannous sulfide micro-flowers that the present invention prepares.
Detailed description of the invention
By the examples below the present invention being described in further details, these embodiments are only used for the present invention is described, do not limit the scope of the invention.
Embodiment 1
The butter of tin of 1mmol is dissolved in 10ml deionized water and forms solution A, the sodium sulfide of 4mmol is dissolved in 20ml deionized water and forms solution B; Then being added dropwise in solution A by solution B, generate yellow mercury oxide, continue dropping, yellow mercury oxide dissolves gradually, eventually forms clear solution. Then add the tetrabutyl ammonium bromide (TBAB) of 5mmol and the thiourea of 4mmol, then final solution is transferred in the stainless steel cauldron that 50ml liner is politef. It is placed in drying baker, hydro-thermal reaction 6 hours at 180 DEG C. Then naturally cool to room temperature, gained precipitate with deionized water and dehydrated alcohol are rinsed three times respectively, centrifugation, 60 DEG C dry 12 hours in vacuum drying oven. Hydro-thermal gained sample is placed in tube furnace, calcines 3 hours at 500 DEG C under nitrogen protection, stannous sulfide (SnS) micro-flowers can be obtained. The X-ray diffractogram of SnS product is shown in that in Fig. 1, figure, each diffraction maximum position and intensity are all consistent with standard diffraction card (JCPDS39-0354). Its scanning electron microscope (SEM) photograph is shown in that Fig. 2, Fig. 2 (a) show that SnS product is size and the comparatively uniform micro-flowers of pattern, average diameter 12.6 ��m. Fig. 2 (b) shows the surface texture of flower-like microsphere, it can be seen that this micro-flowers is made up of many nanometer sheet being staggered.
Embodiment 2
The butter of tin of 1mmol is dissolved in 10ml deionized water and forms solution A, the sodium sulfide of 4mmol is dissolved in 20ml deionized water and forms solution B; Then being added dropwise in solution A by solution B, generate yellow mercury oxide, continue dropping, yellow mercury oxide dissolves gradually, eventually forms clear solution.Then add the tetrabutyl ammonium bromide (TBAB) of 3mmol and the thiourea of 4mmol, then final solution is transferred in the stainless steel cauldron that 50ml liner is politef. It is placed in drying baker, hydro-thermal reaction 4 hours at 170 DEG C. Then naturally cool to room temperature, gained precipitate with deionized water and dehydrated alcohol are rinsed three times respectively, centrifugation, 50 DEG C dry 14 hours in vacuum drying oven. Hydro-thermal gained sample is placed in tube furnace, calcines 2 hours at 400 DEG C under nitrogen protection, stannous sulfide (SnS) micro-flowers can be obtained. The scanning electron microscope (SEM) photograph of SnS product is shown in that Fig. 3, Fig. 3 show that SnS product is size and the comparatively uniform micro-flowers of pattern, and average diameter is 8.3 ��m.
Embodiment 3
The butter of tin of 0.5mmol is dissolved in 10ml deionized water and forms solution A, the sodium sulfide of 2mmol is dissolved in 20ml deionized water and forms solution B; Then being added dropwise in solution A by solution B, generate yellow mercury oxide, continue dropping, yellow mercury oxide dissolves gradually, eventually forms clear solution. Then add the tetrabutyl ammonium bromide (TBAB) of 2mmol and the thiourea of 2mmol, then final solution is transferred in the stainless steel cauldron that 50ml liner is politef. It is placed in drying baker, hydro-thermal reaction 8 hours at 180 DEG C. Then naturally cool to room temperature, gained precipitate with deionized water and dehydrated alcohol are rinsed three times respectively, centrifugation, 70 DEG C dry 10 hours in vacuum drying oven. Hydro-thermal gained sample is placed in tube furnace, calcines 4 hours at 300 DEG C under nitrogen protection, stannous sulfide (SnS) micro-flowers can be obtained. The average diameter of SnS micro-flowers is 7.4 ��m.
Embodiment 4
The butter of tin of 1.5mmol is dissolved in 10ml deionized water and forms solution A, the sodium sulfide of 6mmol is dissolved in 20ml deionized water and forms solution B; Then being added dropwise in solution A by solution B, generate yellow mercury oxide, continue dropping, yellow mercury oxide dissolves gradually, eventually forms clear solution. Then add the tetrabutyl ammonium bromide (TBAB) of 7.5mmol and the thiourea of 6mmol, then final solution is transferred in the stainless steel cauldron that 50ml liner is politef. It is placed in drying baker, hydro-thermal reaction 8 hours at 170 DEG C. Then naturally cool to room temperature, gained precipitate with deionized water and dehydrated alcohol are rinsed three times respectively, centrifugation, 50 DEG C dry 12 hours in vacuum drying oven. Hydro-thermal gained sample is placed in tube furnace, calcines 2 hours at 500 DEG C under nitrogen protection, stannous sulfide (SnS) micro-flowers can be obtained. The average diameter of SnS micro-flowers is 14.7 ��m.
Embodiment 5
The butter of tin of 1mmol is dissolved in 10ml deionized water and forms solution A, the sodium sulfide of 4mmol is dissolved in 20ml deionized water and forms solution B; Then being added dropwise in solution A by solution B, generate yellow mercury oxide, continue dropping, yellow mercury oxide dissolves gradually, eventually forms clear solution. Then add the tetrabutyl ammonium bromide (TBAB) of 5mmol and the thiourea of 4mmol, then final solution is transferred in the stainless steel cauldron that 50ml liner is politef. It is placed in drying baker, hydro-thermal reaction 10 hours at 160 DEG C. Then naturally cool to room temperature, gained precipitate with deionized water and dehydrated alcohol are rinsed three times respectively, centrifugation, 70 DEG C dry 11 hours in vacuum drying oven. Hydro-thermal gained sample is placed in tube furnace, calcines 3 hours at 400 DEG C under nitrogen protection, stannous sulfide (SnS) micro-flowers can be obtained.The average diameter of SnS micro-flowers is 15.4 ��m.
Claims (2)
1. the preparation method of the three-dimensional stannous sulfide micro-flowers of quaternary ammonium salt auxiliary complex-former synthesis, it is characterised in that: comprise the steps:
(1) being under agitation dissolved in by butter of tin in deionized water and form settled solution A, the addition of butter of tin is the molar concentration of tin ion is 0.007��0.07mol/L;
(2) being dissolved in deionized water by chelating agent sodium sulfide, obtain solution B, be then added dropwise in solution A by solution B, Mr.'s yellowly precipitates, and continues dropping, and the mol ratio eventually forming clear solution C, chelating agent and tin ion is 4.0 ~ 6.0:1;
(3) under agitation by pattern and structure regulator quaternary ammonium salt tetrabutyl ammonium bromide, sulfur source: thiourea or thioacetamide sulfur source add in solution C and obtain solution D; The mol ratio of pattern and structure regulator and tin ion is 1.0 ~ 6.0:1, and the mol ratio of sulfur source and tin ion is 4.0 ~ 6.0:1;
(4) the reaction system solution D that step (3) obtains is transferred in the stainless steel cauldron that liner is politef, it is placed in drying baker, react 4 ~ 10 hours under 160 ~ 180 DEG C of hydrothermal conditions, then room temperature is naturally cooled to, gained precipitate with deionized water and dehydrated alcohol are rinsed three times respectively, centrifugation and in vacuum drying oven 50 ~ 70 DEG C dry within 10 ~ 14 hours, obtain product;
(5) being placed in tube furnace by products obtained therefrom, 300 ~ 500 DEG C of heat treatments can obtain three-dimensional stannous sulfide micro-flowers for 2 ~ 4 hours under nitrogen protection.
2. the preparation method that a kind of quaternary ammonium salt auxiliary complex-former synthesizes three-dimensional stannous sulfide micro-flowers according to claim 1, it is characterised in that: the method regulates the size of stannous sulfide flower-like microsphere by the mol ratio or response time changing tin ion concentration or pattern and structure regulator and tin ion.
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Non-Patent Citations (4)
| Title |
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| Controlled self-assembly of PbS nanoparticles into macrostar-like hierarchical structures;Guowei Li et al.;《Materials Research Bulletin》;20110317;第1073页第2.2节以及第1075页右栏第1段 * |
| Formation of SnS nanoflowers for lithium ion batteries;Dimitri D. Vaughn H et al.;《Chem. Commun.》;20120501;第5608-5610页 * |
| Hydrothermal synthesis, characterization and properties of SnS nanoflowers;Hongling Zhu et al.;《Materials Letters》;20060210;第2687页第2部分以及图2 * |
| Shape selective hydrothermal synthesis of tin sulfide nanoflowers based on nanosheets in the presence of thioglycolic acid;Masoud Salavati-Niasari et al.;《Journal of Alloys and Compounds》;20091202;第570–575页 * |
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