CN102701270A - Preparation method for colloidal stannic sulfide hollow nanoparticles - Google Patents
Preparation method for colloidal stannic sulfide hollow nanoparticles Download PDFInfo
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- CN102701270A CN102701270A CN2012101927167A CN201210192716A CN102701270A CN 102701270 A CN102701270 A CN 102701270A CN 2012101927167 A CN2012101927167 A CN 2012101927167A CN 201210192716 A CN201210192716 A CN 201210192716A CN 102701270 A CN102701270 A CN 102701270A
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Abstract
The invention discloses a preparation method for colloidal stannic sulfide hollow nanoparticles. The preparation method comprises the steps as follows: taking a block-shaped metal tin target as a raw material; placing the block-shaped metal tin target into a sulfur source-containing ethanol solution; and controllably synthesizing the high-purity colloidal stannic sulfide (SnS) hollow nanoparticles by utilizing a millisecond laser and chemical etching method in a liquid phase according to the characteristic of the surface reaction of the sputtered metal nanometer liquid drops and the surrounding liquid medias in the long-pulse millisecond laser liquid phase ablation technology. The preparation method is simple in process, convenient to operate and easy to control, doesn't have byproducts and impurities, belongs to normal pressure and temperature synthesis, and is an environment-friendly green synthesis process.
Description
Technical field
The present invention relates to tin sulfide (SnS) hollow Nano particulate, particularly a kind of preparation method of tin sulfide hollow Nano pearl glue liquid solution.
Background technology
Stanniferous chalcogen compound has the good optical activity as a kind of narrow gap semiconductor near infrared, infrared range of spectrum, having a extensive future of infrared optics field; Referring to: Y.Xu, N.Al-Salim, C.W.Bumby et al; Journal of the American Chemical Society; 2009,131,15990-15991.In addition, stanniferous chalcogen compound is one type of nontoxic, eco-friendly material, is expected to become the desirable equivalent material of deleterious narrow bandgap semiconductor material such as PbS, PbSe, PbTe, referring to: J.Ning; K.Men, G.Xiao et al, Nanoscale; 2010,2,1699-1703.In the chalcogen compound of tin, tin sulfide (SnS) has stable stratiform orthorhombic body structure, and direct band gap is 1.3eV, can absorb sunshine effectively.Therefore, the SnS semiconductor material is widely used in fields such as near infrared detector, electrochemical capacitor, lithium ion battery, photovoltaic cell.
Over past ten years, the hollow Nano particle becomes the research focus of field of nanometer technology gradually because of its excellent performance and wide application prospect in addition.Hollow Nano particle wall thickness is a nano level, and the internal space proportion is very big, has characteristics such as density is low, specific surface area is high, thermal expansivity is low, specific refractory power is low, referring to: X.W.Lou; A.Archer, and Z.Yang, Advanced Materials; 2008,20,3987-4019.Therefore, the hollow Nano particle has a good application prospect in fields such as controlled release, catalyzer and the support of the catalyst equal energy source of high performance lithium ion battery, gas sensor, cell angiographic diagnosis, medicine/gene, industrial production control and environmental safety detection, biomedicines.According to the formation mechanism of hollow structure, hollow Nano particulate preparation method can be divided into several following four types: Ke Kendaer (Kirkendall) effect, chemical etching method, Jia Er Giovanni (galvanic) reduction method, template.Wherein, chemical etching method is a kind of easy, hollow Nano particulate compound method efficiently.For example, people such as Ceng Haibo adopt the method for selective etch to obtain oxide compound hollow Nano particle, referring to: H.B.Zeng, W.P.Cai, P.S.Liu et al, Acs Nano, 2008,2,1661-1670; People such as Hyeon adopt the method for heating etching to synthesize various oxide compound hollow Nano particles, referring to: K.An, S.G.Kwon, M.Park et al, Nano Letters, 2008,8,4252-4258.
So far, people adopt chemical method to prepare multiple SnS nanostructure, as, solid nano particle, nano belt, nano wire, nanometer sheet or the like.But SnS hollow Nano particulate preparation does not appear in the newspapers as yet, this be because, SnS nanostructure synthetic adopted traditional solvent thermal or hot method for implanting mostly, its forming core process of growth makes and finally obtains solid nanostructure.
Summary of the invention
The object of the invention; Be to solve existing synthesis technique to fail to obtain tin sulfide hollow Nano particulate problem; Utilize splash-proofing sputtering metal nano-liquid droplet and the characteristics of surrounding liquid medium generation surface reaction in the long pulse millisecond laser liquid phase ablation technology, a kind of millisecond laser and chemical etching method controlledly synthesis high purity colloid tin sulfide (SnS) hollow Nano particulate method in liquid phase, utilized is provided.
The present invention is achieved through following technical scheme.
A kind of colloid tin sulfide hollow Nano particulate preparation method has following steps:
(1) be raw material with reguline metal tin target, tin target purity is 99.99%;
(2) the tin target is placed the ethanolic soln in sulfur-bearing source, its concentration is 0.1～2.0M; Use long pulse millisecond pulse laser bombardment tin target; Wherein laser spot converges at tin target surface; The every 10min of laser irradiation collects and once contains Sn/SnS core-shell nano particulate suspension-s, adds the ethanolic soln in the sulfur-bearing source of same concentrations again, and carries out next batch and synthesize; In the laser irradiation tin target process, adopt argon gas to protect;
(3) to the product of collecting after the laser irradiation purify, drying, obtain highly purified tin/tin sulfide core-shell nano particle powder;
(4) tin/tin sulfide core-shell nano particle powder is dispersed in the ethanol, and is 2.5～3.0 Hydrogen chloride to wherein adding pH value; When treating that solution is become colorless by dark-brown, promptly obtain highly purified colloid tin sulfide hollow Nano particle.
The target thickness of said step (1) is 5mm.
The liquid in the sulfur-bearing source of said step (2) is the ethanolic soln of thioacetamide, and its concentration is 0.1～2.0M; During tin target in the described millisecond pulse laser irradiation liquid medium, the power density of laser is 10
6W/cm
2, laser pulse width is 1.5ms, laser repetition rate is 5Hz; Distance between tin target upper surface and the liquid level is 5mm; Adopt the electromigration platform to move target in the laser irradiation process, with the irradiation position on the continuous change target.
The flow velocity of the argon gas of said step (2) is 60sccm.
The purification process of said step (3) is that product is carried out the 12000rpm high speed centrifugation, and cleans 3 times with ethanol.
The invention has the beneficial effects as follows; Solve existing synthesis technique and failed to obtain tin sulfide (SnS) hollow Nano particulate problem; Realized in the liquid phase at normal temperatures and pressures that colloid SnS hollow Nano particle controlled is synthetic, obtained purity height, good dispersibility, even size distribution, subsphaeroidal SnS hollow Nano pearl glue liquid solution that shell thickness is adjustable.In addition, the synthetic method craft that the present invention adopted is simple, easy to operate, be easy to control, no coupling product and impurity, and it is synthetic to belong to normal temperature and pressure, and the poisonous reaction raw materials of less use, is a kind of eco-friendly green synthesis process.
Description of drawings
Fig. 1 is for utilizing millisecond laser liquid phase ablating technics and chemical etching method controlledly synthesis high purity colloid tin sulfide (SnS) hollow Nano particulate process flow diagram;
Fig. 2 (a) is a SnS hollow Nano particulate low power transmission electron microscope photo;
Fig. 2 (b) is a SnS hollow Nano particulate high resolution transmission electron microscopy photo;
Fig. 2 (c) is a SnS hollow Nano particulate SEAD spectrum;
Fig. 2 (d) is SnS hollow Nano particulate line sweep energy spectrum analysis figure;
Fig. 3 is the transmission electron microscope photo of SnS hollow Nano particle shell layer thickness with thioacetamide (TAA) concentration change rule;
The a1-d1 of Fig. 3 is respectively TAA concentration 0.1M, 0.5M, 1.0M, the resulting Sn/SnS core-shell nano particulate low power transmission electron microscope photo with different shell thicknesses of 2.0M, and scale is represented 20nm among the figure;
The a2-d2 of Fig. 3 is respectively the corresponding high resolution transmission electron microscopy photo of a1-d1, and scale is represented 5nm among the figure;
The a3-d3 of Fig. 3 is respectively the SnS hollow Nano particulate high resolution transmission electron microscopy photo with different shell thicknesses that obtains behind the chemical etching Sn/SnS core-shell nano particle, and scale is represented 5nm among the figure.
Embodiment
Shown in Fig. 1 (a); With purity be 99.99%, the tin target of thickness 5mm places the ethanolic soln of 12mL thioacetamide (TAA); Liquid level and tin target upper surface distance are about 5mm, and adopt the millisecond Pulse Nd: YAG laser (fundamental frequency 1064nm) focusing radiation target surface, laser power density is 10
6W/cm
2, pulsewidth 1.5ms, repetition rate 5Hz.Laser irradiation process employing flow velocity is that the argon gas stream of 60sccm is protected, and prevents tin generation oxidation.
In the long pulse millisecond laser irradiation liquid medium during tin target, because its power density (10
6W/cm
2) than the power density (10 of nanosecond laser
8-10
10W/cm
2) low at least two one magnitude; Therefore; Millisecond laser can carry out gentle relatively heating and sputter out many sijna rice drops from target surface the target surface irradiated site; Surperficial vulcanization reaction takes place with on every side TAA ethanolic soln in sijna rice drop in process of cooling, form tin/tin sulfide core-shell nano particle.
Adopt the electromigration platform to move target in the laser irradiation process,, its objective is that the pit of avoiding on the target surface influences the sputter of follow-up sijna rice drop with the irradiation position on the continuous change target.Collect product in batches, collect a product (product is for containing Sn/SnS core-shell nano particulate suspension-s) about promptly every irradiation 10min, add the TAA ethanolic soln of same concentrations again and carry out next batch and synthesize.
Product is carried out high speed centrifugation, and centrifugal rotational speed is 12000rpm, and cleans 3 times, drying with ethanol, at last gained Sn/SnS core-shell nano particle powder is dispersed in the ethanol, shown in Fig. 1 (b).Get 2mL Sn/SnS core-shell nano particulate ethanolic soln; To the pH value that wherein adds 1mL 2.5～3.0 Hydrogen chloride; This Hydrogen chloride can etch away Sn nuclear and not react with the SnS shell; When treating that solution is become colorless by dark-brown, promptly obtain highly purified SnS hollow Nano pearl glue liquid solution, shown in Fig. 1 (c).Low power transmission electron microscope photo by Fig. 2 (a) can find out that SnS hollow Nano particle size is even, and is better dispersed; The high resolution transmission microscopy photo of Fig. 2 (b) shows that SnS hollow Nano particle has subglobose pattern, and crystallinity is good; Fig. 2 (c) to choose the electron-diffraction diagram stave bright, the quadrature of SnS hollow Nano particulate polycrystalline diffraction pattern and SnS crystalline structure mutually is consistent; The line sweep of Fig. 2 (d) can point out that SnS hollow Nano particulate shell is elementary composition by Sn and S by spectrogram.For the Hydrogen chloride of different PH (2.5～3.0), its effect has not been found obvious difference.
It should be noted that if adopt the Hydrogen chloride of PH＜2.5 then Sn nuclear, SnS shell all can be by the Hydrogen chloride etchings, and can not obtain SnS hollow Nano particle.
Through regulating the concentration of TAA, can effectively regulate SnS hollow Nano particulate shell thickness.For example; When TAA concentration is respectively 0.1M, 0.5M, 1.0M, 2.0M; Can find out by the low power transmission electron microscope photo of Fig. 3 (a1-d1) and the high resolution transmission electron microscopy photo of Fig. 3 (a2-d2), obtain having the Sn/SnS core-shell nano particle of different shell thicknesses respectively; Above Sn/SnS core-shell nano particle is behind chemical etching; Obtain the SnS hollow Nano particle shown in Fig. 3 (a3-d3) respectively with different shell thicknesses; SnS hollow Nano particulate shell thickness is respectively 3.8nm, 4.5nm, 6.0nm, 7.0nm; That is, SnS hollow Nano particulate shell thickness increases with the increase of TAA concentration.
In sum; Adopt long pulse millisecond laser liquid phase ablation technology and chemical etching method can liquid phase at normal temperatures and pressures in controlledly synthesis colloid tin sulfide (SnS) hollow Nano particle, characteristics such as nano particle has purity height, good dispersibility, even size distribution, shell thickness is adjustable.
Claims (5)
1. colloid tin sulfide hollow Nano particulate preparation method has following steps:
(1) be raw material with reguline metal tin target, tin target purity is 99.99%;
(2) the tin target is placed the ethanolic soln in sulfur-bearing source, its concentration is 0.1～2.0M; Use long pulse millisecond pulse laser bombardment tin target; Wherein laser spot converges at tin target surface; The every 10min of laser irradiation collects and once contains Sn/SnS core-shell nano particulate suspension-s, adds the ethanolic soln in the sulfur-bearing source of same concentrations again, and carries out next batch and synthesize; In the laser irradiation tin target process, adopt argon gas to protect;
(3) to the product of collecting after the laser irradiation purify, drying, obtain highly purified tin/tin sulfide core-shell nano particle powder;
(4) tin/tin sulfide core-shell nano particle powder is dispersed in the ethanol, and is 2.5～3.0 Hydrogen chloride to wherein adding pH value; When treating that solution is become colorless by dark-brown, promptly obtain highly purified colloid tin sulfide hollow Nano particle.
2. according to the colloid tin sulfide hollow Nano particulate preparation method of claim 1, it is characterized in that the target thickness of said step (1) is 5mm.
3. according to the colloid tin sulfide hollow Nano particulate preparation method of claim 1, it is characterized in that the liquid in the sulfur-bearing source of said step (2) is the ethanolic soln of thioacetamide, its concentration is 0.1～2.0M; During tin target in the described millisecond pulse laser irradiation liquid medium, the power density of laser is 10
6W/cm
2, laser pulse width is 1.5ms, laser repetition rate is 5Hz; Distance between tin target upper surface and the liquid level is 5mm; Adopt the electromigration platform to move target in the laser irradiation process, with the irradiation position on the continuous change target.
4. according to the colloid tin sulfide hollow Nano particulate preparation method of claim 1, it is characterized in that the flow velocity of the argon gas of said step (2) is 60sccm.
5. according to the colloid tin sulfide hollow Nano particulate preparation method of claim 1, it is characterized in that the purification process of said step (3) is that product is carried out the 12000rpm high speed centrifugation, and clean 3 times with ethanol.
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Cited By (4)
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|---|---|---|---|---|
| CN103359685A (en) * | 2013-07-02 | 2013-10-23 | 中山大学 | Positioning and doping method for nanomaterial |
| CN104549292A (en) * | 2015-03-02 | 2015-04-29 | 天津大学 | Technological method for preparing nickel/silicon dioxide supported catalyst by laser liquid phase |
| CN106645805A (en) * | 2016-12-28 | 2017-05-10 | 西安交通大学青岛研究院 | Method of carrying out laser liquid phase ablation test by using laser liquid phase ablation system |
| CN107703169A (en) * | 2016-12-28 | 2018-02-16 | 西安交通大学青岛研究院 | A kind of experimental provision of the laser ablation nanostructured monitored in real time |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103359685A (en) * | 2013-07-02 | 2013-10-23 | 中山大学 | Positioning and doping method for nanomaterial |
| CN103359685B (en) * | 2013-07-02 | 2016-04-13 | 中山大学 | A kind of location doping method of nano material |
| CN104549292A (en) * | 2015-03-02 | 2015-04-29 | 天津大学 | Technological method for preparing nickel/silicon dioxide supported catalyst by laser liquid phase |
| CN106645805A (en) * | 2016-12-28 | 2017-05-10 | 西安交通大学青岛研究院 | Method of carrying out laser liquid phase ablation test by using laser liquid phase ablation system |
| CN107703169A (en) * | 2016-12-28 | 2018-02-16 | 西安交通大学青岛研究院 | A kind of experimental provision of the laser ablation nanostructured monitored in real time |
| CN106645805B (en) * | 2016-12-28 | 2019-11-19 | 青岛华通检测评价有限公司 | A method of laser liquid phase ablation test is carried out using laser liquid phase ablation system |
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