CN102502792A - Preparation method of spherical SnS nanometer crystals - Google Patents

Preparation method of spherical SnS nanometer crystals Download PDF

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CN102502792A
CN102502792A CN2011103758879A CN201110375887A CN102502792A CN 102502792 A CN102502792 A CN 102502792A CN 2011103758879 A CN2011103758879 A CN 2011103758879A CN 201110375887 A CN201110375887 A CN 201110375887A CN 102502792 A CN102502792 A CN 102502792A
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CN102502792B (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

The nanocrystalline preparation method of a kind of spherical SnS
Technical field
The present invention relates to a kind of preparation method of SnS nano-powder, be specifically related to a kind of microwave hydrothermal that adopts and prepare the nanocrystalline method of spherical SnS.
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 cost, people with polysilicon, silicon grain, chalcogenide (like CdS, CdTe, CIS ...) etc. substituted single crystal silicon.In order to improve photoelectric transformation efficiency; People adopt on the one hand and select more superior novel photoelectric material such as GaAs, the InP etc. of performance; Adopt some new battery structures on the other hand; Modal is with means such as chemical corrosions battery surface to be carried out 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 that Sn and S element earth content enrich, and nontoxic.The optics direct band gap of SnS is 1.2～1.5eV in addition, and fabulous with the visible light coupling, its photoelectric transformation efficiency can reach 25%, is suitable as very much the light absorbing zone in the solar cell.Therefore, as a kind of novel photoelectric transition material with potential application foreground, SnS receives people's attention in recent years gradually with its abundant earth reserves and the inherent characteristics of material itself.
At present SnS nano wire [Yingkai Liu, Dedong Hou, Guanghou Wang.Chemical PhysicsLetters, 379 (2003) 67-73.], nanometer rod [H.L.Su have been prepared through different preparation technologies success; 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. have a powder of special appearance.These unique nanostructures explain that undoubtedly the SnS thing has the material of abundant structures and character, but do not see the report about the SnS nanometer ball so far.
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 prepares the nanocrystalline method of spherical SnS; Can prepare the spheroidal particle that particle diameter of nanometer powder is 10～30nm by preparation method of the present invention, be uniformly dispersed and purity higher.
For achieving the above object, the technical scheme that the present invention adopts is:
1) with analytically pure SnCl 22H 2O is dissolved in the concentrated hydrochloric acid, adds deionized water again and is mixed with Sn 2+Concentration is the clear solution A of 0.005mol/L～0.5mol/L;
2) with analytically pure (NH 4) 2S solution adds deionized water and is mixed with S 2-Concentration is the yellow solution B of 0.001mol/L～1.0mol/L;
The solution A of 3) getting 25ml is processed solution C to the analytically pure polyoxyethylene glycol (PEG) that wherein adds 0.1～2g;
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 the hydrothermal reaction kettle, compactedness is controlled at 40%～80%; The sealing hydrothermal reaction kettle puts it in the two control of the temperature and pressure 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, and reaction naturally cools to room temperature after finishing;
6) open hydrothermal reaction kettle, product adopts deionized water and absolute ethyl alcohol or washed with isopropyl alcohol respectively then through centrifugal collection, places vacuum drying oven after 40 ℃～70 ℃ following dryings, to get the spherical SnS nanocrystal of final product again.
Described analytically pure (NH 4) 2The S of S solution 2-Concentration>=8%.
The present invention adopts microwave-hydrothermal method, prepares the spherical SnS nanocrystal of even particle size fast, once accomplishes owing to be reflected in the liquid phase, do not need post-processed, and processing unit is simple, and reaction time is short.
Description of drawings
Fig. 1 is prepared nanocrystalline X-ray diffraction (XRD) collection of illustrative plates of spherical SnS of the embodiment of the invention 1;
Fig. 2 is the prepared nanocrystalline TEM photo of spherical SnS of the embodiment of the invention 1.
Embodiment
Below in conjunction with accompanying drawing and embodiment the present invention is done further explain.
Embodiment 1:
1) with analytically pure SnCl 22H 2O is dissolved in the concentrated hydrochloric acid, adds deionized water again and is mixed with Sn 2+Concentration is the clear solution A of 0.005mol/L;
2) with analytically pure S 2-(the NH of concentration>=8% 4) 2S solution adds deionized water and is mixed with S 2-Concentration is the yellow solution B of 0.001mol/L;
The solution A of 3) getting 25ml is processed solution C to the analytically pure polyoxyethylene glycol (PEG) that wherein adds 0.1g;
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 the hydrothermal reaction kettle, compactedness is controlled at 70%; The sealing hydrothermal reaction kettle puts it in the two control of the temperature and pressure 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, and reaction naturally cools to room temperature after finishing;
6) open hydrothermal reaction kettle, product adopts deionized water and absolute ethanol washing respectively then through centrifugal collection, places vacuum drying oven after 40 ℃ of following dryings, to get the spherical SnS nanocrystal of final product again.
The spherical SnS nanocrystal of gained is analyzed with Japanese D/max2000PC x-ray diffractometer of science; The discovery product is rhombic form (Fig. 1); At 2 θ is 30.478 °, 31.579 °, and 31.903 °; 39.059 ° locate diffraction peak, the crystal face of corresponding SnS is (101), (111), (040), (131).Sample with observing (Fig. 2) with the TEM-3010 of Jeol Ltd. (JEOL) type transmission electron microscope, can be found out prepared SnS nano crystal particles size evenly from photo, be approximately 20nm.
Embodiment 2:
1) with analytically pure SnCl 22H 2O is dissolved in the concentrated hydrochloric acid, adds deionized water again and is mixed with Sn 2+Concentration is the clear solution A of 0.01mol/L;
2) with analytically pure S 2-(the NH of concentration>=8% 4) 2S solution adds deionized water and is mixed with S 2-Concentration is the yellow solution B of 0.05mol/L;
The solution A of 3) getting 25ml is processed solution C to the analytically pure polyoxyethylene glycol (PEG) that wherein adds 0.8g;
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 the hydrothermal reaction kettle, compactedness is controlled at 60%; The sealing hydrothermal reaction kettle puts it in the two control of the temperature and pressure 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, and reaction naturally cools to room temperature after finishing;
6) open hydrothermal reaction kettle, product adopts deionized water and washed with isopropyl alcohol respectively then through centrifugal collection, places vacuum drying oven after 60 ℃ of following dryings, to get the spherical SnS nanocrystal of final product again.
Embodiment 3:
1) with analytically pure SnCl 22H 2O is dissolved in the concentrated hydrochloric acid, adds deionized water again and is mixed with Sn 2+Concentration is the clear solution A of 0.2mol/L;
2) with analytically pure S 2-(the NH of concentration>=8% 4) 2S solution adds deionized water and is mixed with S 2-Concentration is the yellow solution B of 0.1mol/L;
The solution A of 3) getting 25ml is processed solution C to the analytically pure polyoxyethylene glycol (PEG) that wherein adds 1.5g;
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 the hydrothermal reaction kettle, compactedness is controlled at 50%; The sealing hydrothermal reaction kettle puts it in the two control of the temperature and pressure 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, and reaction naturally cools to room temperature after finishing;
6) open hydrothermal reaction kettle, product adopts deionized water and absolute ethanol washing respectively then through centrifugal collection, places vacuum drying oven after 70 ℃ of following dryings, to get the spherical SnS nanocrystal of final product again.
Embodiment 4:
1) with analytically pure SnCl 22H 2O is dissolved in the concentrated hydrochloric acid, adds deionized water again and is mixed with Sn 2+Concentration is the clear solution A of 0.2ol/L;
2) with analytically pure S 2-(the NH of concentration>=8% 4) 2S solution adds deionized water and is mixed with S 2-Concentration is the yellow solution B of 0.6mol/L;
The solution A of 3) getting 25ml is processed solution C to the analytically pure polyoxyethylene glycol (PEG) that wherein adds 2g;
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 the hydrothermal reaction kettle, compactedness is controlled at 40%; The sealing hydrothermal reaction kettle puts it in the two control of the temperature and pressure 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, and reaction naturally cools to room temperature after finishing;
6) open hydrothermal reaction kettle, product adopts deionized water and washed with isopropyl alcohol respectively then through centrifugal collection, places vacuum drying oven after 50 ℃ of following dryings, to get the spherical SnS nanocrystal of final product again.
Embodiment 5:
1) with analytically pure SnCl 22H 2O is dissolved in the concentrated hydrochloric acid, adds deionized water again and is mixed with Sn 2+Concentration is the clear solution A of 0.5mol/L;
2) with analytically pure S 2-(the NH of concentration>=8% 4) 2S solution adds deionized water and is mixed with S 2-Concentration is the yellow solution B of 1.0mol/L;
The solution A of 3) getting 25ml is processed solution C to the analytically pure polyoxyethylene glycol (PEG) that wherein adds 0.5g;
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 the hydrothermal reaction kettle, compactedness is controlled at 80%; The sealing hydrothermal reaction kettle puts it in the two control of the temperature and pressure 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, and reaction naturally cools to room temperature after finishing;
6) open hydrothermal reaction kettle, product adopts deionized water and absolute ethanol washing respectively then through centrifugal collection, places vacuum drying oven after 60 ℃ of following dryings, to get the spherical SnS nanocrystal of final product again.

Claims (2)

1. nanocrystalline preparation method of spherical SnS is characterized in that:
1) with analytically pure SnCl 22H 2O is dissolved in the concentrated hydrochloric acid, adds deionized water again and is mixed with Sn 2+Concentration is the clear solution A of 0.005mol/L～0.5mol/L;
2) with analytically pure (NH 4) 2S solution adds deionized water and is mixed with S 2-Concentration is the yellow solution B of 0.001mol/L～1.0mol/L;
The solution A of 3) getting 25ml is processed solution C to the analytically pure polyoxyethylene glycol (PEG) that wherein adds 0.1～2g;
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 the hydrothermal reaction kettle, compactedness is controlled at 40%～80%; The sealing hydrothermal reaction kettle puts it in the two control of the temperature and pressure 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, and reaction naturally cools to room temperature after finishing;
6) open hydrothermal reaction kettle, product adopts deionized water and absolute ethyl alcohol or washed with isopropyl alcohol respectively then through centrifugal collection, places vacuum drying oven after 40 ℃～70 ℃ following dryings, to get the spherical SnS nanocrystal of final product again.
2. the nanocrystalline preparation method of spherical SnS 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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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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
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
CN105016378A (en) * 2014-04-21 2015-11-04 渤海大学 Preparation method of tin sulfide nanosheet
CN107177887A (en) * 2017-06-26 2017-09-19 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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CN101609886A (en) * 2009-07-16 2009-12-23 浙江大学 A kind of preparation lithium ion battery SnO 2/ SnS 2The method of nanometer combined electrode material
CN101844799A (en) * 2010-06-17 2010-09-29 安阳师范学院 Preparation method of hexagon stannic disulphide nano slice
CN101950804A (en) * 2010-07-14 2011-01-19 北京理工大学 Method for preparing spherical SnS2 anode material of lithium ion battery

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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
CN101609886A (en) * 2009-07-16 2009-12-23 浙江大学 A kind of preparation lithium ion battery SnO 2/ SnS 2The method of nanometer combined electrode material
CN101844799A (en) * 2010-06-17 2010-09-29 安阳师范学院 Preparation method of hexagon stannic disulphide nano slice
CN101950804A (en) * 2010-07-14 2011-01-19 北京理工大学 Method for preparing spherical SnS2 anode material of lithium ion battery

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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
CN105016378A (en) * 2014-04-21 2015-11-04 渤海大学 Preparation method of tin sulfide nanosheet
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
CN107177887A (en) * 2017-06-26 2017-09-19 陕西科技大学 A kind of room temperature water solution growth stannous selenide nanometer rods cone monocrystalline and its method
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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