CN102502792B - Preparation method of spherical SnS nanometer crystals - Google Patents

Preparation method of spherical SnS nanometer crystals Download PDF

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CN102502792B
CN102502792B CN201110375887.9A CN201110375887A CN102502792B CN 102502792 B CN102502792 B CN 102502792B CN 201110375887 A CN201110375887 A CN 201110375887A CN 102502792 B CN102502792 B CN 102502792B
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CN102502792A (en
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黄剑锋
张培培
齐慧
曹丽云
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Qidong Xincheng New Material Technology Co.,Ltd.
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Shaanxi University of Science and Technology
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Abstract

The invention relates to a preparation method of spherical SnS nanometer crystals. The preparation method comprises the steps of: dissolving SnCl2.2H2O in concentrated hydrochloric acid, and adding de-ionized water to obtain a solution A; adding an (NH4)2S solution into the de-ionized water to prepare a solution B; adding polyethylene glycol into the solution A to prepare a solution C; dropwise adding the solution B into the solution C to form a precursor solution D; pouring the solution D into a hydro-thermal reaction kettle, placing the hydro-thermal reaction kettle into a temperature and pressure control microwave hydro-thermal reaction instrument for hydro-thermal reaction; opening the hydro-thermal reaction kettle, collecting the product by centrifuging, then washing by using the de-ionized water and absolute ethanol or isopropanol respectively, and then drying in a vacuum dry box to obtain the spherical SnS nanometer crystals as final products. According to the preparation method, the spherical SnS nanometer crystals with uniform particle sizes are quickly prepared by using a microwave hydro-thermal method; as the reaction is once finished in a liquid phase, the post treatment is not required; and simple process equipment and short reaction cycle are realized.

Description

A kind of spherical SnS nanometer crystals preparation method
Technical field
The present invention relates to a kind of preparation method of SnS nano-powder, be specifically related to a kind of method that adopts microwave hydrothermal to prepare spherical SnS nanometer crystals.
Background technology
Reducing manufacturing cost, improving photoelectric transformation efficiency is that solar cell development research person pays close attention to two research topics the most always.In order to reduce costs, people use polysilicon, silicon grain, chalcogenide (as CdS, CdTe, CIS ...) etc. substituted single crystal silicon.In order to improve photoelectric transformation efficiency, people adopt novel photoelectric material that selectivity is more superior as GaAs, InP etc. on the one hand, adopt on the other hand some new battery structures, modal is, by means such as chemical corrosions, battery surface is carried out to texturing or porous, utilizes and falls into the photoabsorption that light effect increases solar cell.
In the middle of chalcogenide, Cd is poisonous element, and Te and In are rare elements.By contrast, the advantage of SnS material is Sn and S element earth rich content, and nontoxic.In addition the optics direct band gap of SnS is 1.2～1.5eV, mates fabulously with visible light, and its photoelectric transformation efficiency can reach 25%, is suitable as very much the light absorbing zone in solar cell.Therefore,, as a kind of novel photoelectric transition material with potential application foreground, SnS, with the inherent characteristics of its abundant earth reserves and material itself, is subject to people's attention in recent years gradually.
At present by different preparation technologies, successfully prepared SnS nano wire [Yingkai Liu, Dedong Hou, Guanghou Wang.Chemical PhysicsLetters, 379 (2003) 67-73.], nanometer rod [H.L.Su, Y.Xie, Y.J.Xiong, P.Gao, Y.T.Qian, J.Solid State Chem.161 (2001) 190-196.], nano belt [C.H.An, K.B.Tang, G.Z.Shen, C.R.Wang, Q.Yang, B.Hai, Y.T.Qian, J.Crystal Growth 244 (2002) 333-338.], soccerballene [S.Y.Hong, R.Popovitz-Biro, Y.Prior, R.Tenne, J.Am.Chem.Soc.125 (2005) 10470-10474.], nanometer sheet [Guozhen Shen, Di Chen, Kaibin Tang, LiyingHuang, et al.Inorganic Chemistry Communications.6 (2003) 178-180.] etc. there is the powder of special appearance.These unique nanostructures illustrate that SnS thing has the material of abundant structure and character undoubtedly, but so far there are no about the report of SnS nanometer ball.
Summary of the invention
The object of the invention is to provide a kind of equipment simple, easy handling, preparation time is short, and the microwave-hydrothermal method that cost is low is prepared the method for spherical SnS nanometer crystals, by preparation method of the present invention, can prepare the spheroidal particle that particle diameter of nanometer powder is 10～30nm, be uniformly dispersed and purity higher.
For achieving the above object, the technical solution used in the present invention is:
1) by analytically pure SnCl 22H 2o is dissolved in concentrated hydrochloric acid, then adds deionized water to be mixed with Sn 2+concentration is the clear solution A of 0.005mol/L～0.5mol/L;
2) by analytically pure (NH 4) 2s solution adds deionized water to be mixed with S 2-concentration is the yellow solution B of 0.001mol/L～1.0mol/L;
3) solution A of getting 25ml adds the analytically pure polyoxyethylene glycol (PEG) of 0.1～2g to make solution C wherein;
4) under magnetic agitation, in C solution, drip solution B, make Sn 2+: S 2-mol ratio be 1: (1～10) forms precursor solution D;
5) solution D is poured in hydrothermal reaction kettle, compactedness is controlled at 40%～80%; Sealing hydrothermal reaction kettle, puts it in warm-pressing double-control microwave hydrothermal reaction; Select temperature controlling mode to react, hydrothermal temperature is controlled at 100 ℃～180 ℃, and pressure is less than 3.0MPa, and the reaction times is controlled at 10min～120min, after reaction finishes, naturally cools to room temperature;
6) open hydrothermal reaction kettle, product, by centrifugal collection, then adopts respectively deionized water and dehydrated alcohol or washed with isopropyl alcohol, then be placed in vacuum drying oven after dry at 40 ℃～70 ℃ final product spherical SnS nanometer crystals body.
Described analytically pure (NH 4) 2the S of S solution 2-concentration>=8%.
The present invention adopts microwave-hydrothermal method, prepares fast the spherical SnS nanometer crystals body of even particle size, because reaction once completes in liquid phase, do not need post-processed, and processing unit is simple, and reaction time is short.
Accompanying drawing explanation
Fig. 1 is X-ray diffraction (XRD) collection of illustrative plates of the prepared spherical SnS nanometer crystals of the embodiment of the present invention 1;
Fig. 2 is the TEM photo of the prepared spherical SnS nanometer crystals of the embodiment of the present invention 1.
Embodiment
Below in conjunction with drawings and Examples, the present invention is described in further detail.
Embodiment 1:
1) by analytically pure SnCl 22H 2o is dissolved in concentrated hydrochloric acid, then adds deionized water to be mixed with Sn 2+concentration is the clear solution A of 0.005mol/L;
2) by analytically pure S 2-(the NH of concentration>=8% 4) 2s solution adds deionized water to be mixed with S 2-concentration is the yellow solution B of 0.001mol/L;
3) solution A of getting 25ml adds the analytically pure polyoxyethylene glycol (PEG) of 0.1g to make solution C wherein;
4) under magnetic agitation, in C solution, drip solution B, make Sn 2+: S 2-mol ratio be to form precursor solution D at 1: 2;
5) solution D is poured in hydrothermal reaction kettle, compactedness is controlled at 70%; Sealing hydrothermal reaction kettle, puts it in warm-pressing double-control microwave hydrothermal reaction; Select temperature controlling mode to react, hydrothermal temperature is controlled at 100 ℃, and pressure is less than 3.0MPa, and the reaction times is controlled at 120min, after reaction finishes, naturally cools to room temperature;
6) open hydrothermal reaction kettle, product, by centrifugal collection, then adopts respectively deionized water and absolute ethanol washing, then be placed in vacuum drying oven after dry at 40 ℃ final product spherical SnS nanometer crystals body.
The spherical SnS nanometer crystals body of gained is analyzed with Rigaku D/max2000PC x-ray diffractometer, discovery product is rhombic form (Fig. 1), at 2 θ, it is 30.478 °, 31.579 °, 31.903 °, locate diffraction peak for 39.059 °, the crystal face of corresponding SnS is (101), (111), (040), (131).The TEM-3010 of sample Yong Yong Jeol Ltd. (JEOL) type transmission electron microscope is observed to (Fig. 2), from photo, can find out prepared SnS nano crystal particles size evenly, be approximately 20nm.
Embodiment 2:
1) by analytically pure SnCl 22H 2o is dissolved in concentrated hydrochloric acid, then adds deionized water to be mixed with Sn 2+concentration is the clear solution A of 0.01mol/L;
2) by analytically pure S 2-(the NH of concentration>=8% 4) 2s solution adds deionized water to be mixed with S 2-concentration is the yellow solution B of 0.05mol/L;
3) solution A of getting 25ml adds the analytically pure polyoxyethylene glycol (PEG) of 0.8g to make solution C wherein;
4) under magnetic agitation, in C solution, drip solution B, make Sn 2+: S 2-mol ratio be to form precursor solution D at 1: 1;
5) solution D is poured in hydrothermal reaction kettle, compactedness is controlled at 60%; Sealing hydrothermal reaction kettle, puts it in warm-pressing double-control microwave hydrothermal reaction; Select temperature controlling mode to react, hydrothermal temperature is controlled at 120 ℃, and pressure is less than 3.0MPa, and the reaction times is controlled at 80min, after reaction finishes, naturally cools to room temperature;
6) open hydrothermal reaction kettle, product, by centrifugal collection, then adopts respectively deionized water and washed with isopropyl alcohol, then be placed in vacuum drying oven after dry at 60 ℃ final product spherical SnS nanometer crystals body.
Embodiment 3:
1) by analytically pure SnCl 22H 2o is dissolved in concentrated hydrochloric acid, then adds deionized water to be mixed with Sn 2+concentration is the clear solution A of 0.2mol/L;
2) by analytically pure S 2-(the NH of concentration>=8% 4) 2s solution adds deionized water to be mixed with S 2-concentration is the yellow solution B of 0.1mol/L;
3) solution A of getting 25ml adds the analytically pure polyoxyethylene glycol (PEG) of 1.5g to make solution C wherein;
4) under magnetic agitation, in C solution, drip solution B, make Sn 2+: S 2-mol ratio be to form precursor solution D at 1: 5;
5) solution D is poured in hydrothermal reaction kettle, compactedness is controlled at 50%; Sealing hydrothermal reaction kettle, puts it in warm-pressing double-control microwave hydrothermal reaction; Select temperature controlling mode to react, hydrothermal temperature is controlled at 140 ℃, and pressure is less than 3.0MPa, and the reaction times is controlled at 50min, after reaction finishes, naturally cools to room temperature;
6) open hydrothermal reaction kettle, product, by centrifugal collection, then adopts respectively deionized water and absolute ethanol washing, then be placed in vacuum drying oven after dry at 70 ℃ final product spherical SnS nanometer crystals body.
Embodiment 4:
1) by analytically pure SnCl 22H 2o is dissolved in concentrated hydrochloric acid, then adds deionized water to be mixed with Sn 2+concentration is the clear solution A of 0.2ol/L;
2) by analytically pure S 2-(the NH of concentration>=8% 4) 2s solution adds deionized water to be mixed with S 2-concentration is the yellow solution B of 0.6mol/L;
3) solution A of getting 25ml adds the analytically pure polyoxyethylene glycol (PEG) of 2g to make solution C wherein;
4) under magnetic agitation, in C solution, drip solution B, make Sn 2+: S 2-mol ratio be to form precursor solution D at 1: 3;
5) solution D is poured in hydrothermal reaction kettle, compactedness is controlled at 40%; Sealing hydrothermal reaction kettle, puts it in warm-pressing double-control microwave hydrothermal reaction; Select temperature controlling mode to react, hydrothermal temperature is controlled at 160 ℃, and pressure is less than 3.0MPa, and the reaction times is controlled at 30min, after reaction finishes, naturally cools to room temperature;
6) open hydrothermal reaction kettle, product, by centrifugal collection, then adopts respectively deionized water and washed with isopropyl alcohol, then be placed in vacuum drying oven after dry at 50 ℃ final product spherical SnS nanometer crystals body.
Embodiment 5:
1) by analytically pure SnCl 22H 2o is dissolved in concentrated hydrochloric acid, then adds deionized water to be mixed with Sn 2+concentration is the clear solution A of 0.5mol/L;
2) by analytically pure S 2-(the NH of concentration>=8% 4) 2s solution adds deionized water to be mixed with S 2-concentration is the yellow solution B of 1.0mol/L;
3) solution A of getting 25ml adds the analytically pure polyoxyethylene glycol (PEG) of 0.5g to make solution C wherein;
4) under magnetic agitation, in C solution, drip solution B, make Sn 2+: S 2-mol ratio be to form precursor solution D at 1: 10;
5) solution D is poured in hydrothermal reaction kettle, compactedness is controlled at 80%; Sealing hydrothermal reaction kettle, puts it in warm-pressing double-control microwave hydrothermal reaction; Select temperature controlling mode to react, hydrothermal temperature is controlled at 180 ℃, and pressure is less than 3.0MPa, and the reaction times is controlled at 10min, after reaction finishes, naturally cools to room temperature;
6) open hydrothermal reaction kettle, product, by centrifugal collection, then adopts respectively deionized water and absolute ethanol washing, then be placed in vacuum drying oven after dry at 60 ℃ final product spherical SnS nanometer crystals body.

Claims (2)

1. a spherical SnS nanometer crystals preparation method, is characterized in that:
1) by analytically pure SnCl 22H 2o is dissolved in concentrated hydrochloric acid, then adds deionized water to be mixed with Sn 2+concentration is the clear solution A of 0.005mol/L～0.5mol/L;
2) by analytically pure (NH 4) 2s solution adds deionized water to be mixed with S 2-concentration is the yellow solution B of 0.001mol/L～1.0mol/L;
3) solution A of getting 25ml adds the analytically pure polyoxyethylene glycol (PEG) of 0.1～2g to make solution C wherein;
4) under magnetic agitation, in C solution, drip solution B, make Sn 2+: S 2-mol ratio be 1:(1～10) form precursor solution D;
5) solution D is poured in hydrothermal reaction kettle, compactedness is controlled at 40%～80%; Sealing hydrothermal reaction kettle, puts it in warm-pressing double-control microwave hydrothermal reaction; Select temperature controlling mode to react, hydrothermal temperature is controlled at 100 ℃～180 ℃, and pressure is less than 3.0MPa, and the reaction times is controlled at 10min～120min, after reaction finishes, naturally cools to room temperature;
6) open hydrothermal reaction kettle, product, by centrifugal collection, then adopts respectively deionized water and absolute ethanol washing or deionized water and washed with isopropyl alcohol, then be placed in vacuum drying oven after dry at 40 ℃～70 ℃ final product spherical SnS nanometer crystals body.
2. spherical SnS nanometer crystals preparation method according to claim 1, is characterized in that: described analytically pure (NH 4) 2the S of S solution 2-concentration>=8%.
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CN102897827A (en) * 2012-10-09 2013-01-30 东华大学 Method for phased synthesis of SnS, SnS2 or SnS/SnS2 heterojunction nanocrystalline material by one-step process
CN105016378B (en) * 2014-04-21 2016-08-17 渤海大学 The preparation method of stannous sulfide nanometer sheet
CN104201232A (en) * 2014-08-28 2014-12-10 南京大学 Tin sulfide nano paper self-assembly microsphere production method and optical detector of microsphere film
CN107177887B (en) * 2017-06-26 2019-03-26 陕西科技大学 A kind of room temperature water solution growth stannous selenide nanometer rods cone monocrystalline and its method

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CN101609887A (en) * 2009-07-16 2009-12-23 浙江大学 A kind of lithium ion battery SnS 2The preparation method of nanometer sheet negative material
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