CN101955220B - Method for preparing PbS spherical nano crystals by water-phase process - Google Patents
Method for preparing PbS spherical nano crystals by water-phase process Download PDFInfo
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- CN101955220B CN101955220B CN2009100393438A CN200910039343A CN101955220B CN 101955220 B CN101955220 B CN 101955220B CN 2009100393438 A CN2009100393438 A CN 2009100393438A CN 200910039343 A CN200910039343 A CN 200910039343A CN 101955220 B CN101955220 B CN 101955220B
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Abstract
The invention discloses a method for preparing PbS spherical nano crystals by a water-phase process. In the method, lead acetate is used as a raw material and reacted with sodium sulfide under the coactions of the cetyl trimethyl ammonium bromide and tert-dodecanethiol surfactants, and the PbS spherical nano crystals are obtained by separating and purifying. The method adopts industrial raw materials which are cheap and readily available and ensures mild reaction conditions and simple and convenient operation.
Description
Technical field
The present invention relates to the nanocrystal field, particularly a kind of water legal system is equipped with PbS ball shaped nano crystalline method.
Background technology
Nanocrystalline IV～VI family the semiconductor nano (quantum dot) that belongs to of PbS; Has less band gap (0.41eV; 300K) and bigger exciton Bohr radius (18nm); Its electron energy band has the potential purposes in fields such as nonlinear optical device, infrared eye, solar receiver and biomarkers from the visible light to the near infrared region.Based on the nano material of PbS quantum dot, its performance and microscopic appearance are contacted directly.Because the PbS quantum dot is an isotropic material, oriented growth is difficult to control in the preparation process, and the report of spherical nanostructure is less relatively.Some scholar utilizes the synthetic PbS zero-dimension nano structure of tensio-active agent control, like (G.J.Zhou, M.K.L ü such as L ü; Z.L.Xiu, S.F.Wang, H.P.Zhang; Y.Y.Zhou; S.M.Wang.J.Phys.Chem.B 2006,110,6543) with plumbic acetate be plumbous source, thioacetyl ammonium (TAA) be the sulphur source 100 ℃ of tensio-active agent cetyl trimethylammonium bromides (CTAB), temperature of reaction down reaction obtain spherical PbS nanoparticle after 30 minutes; But the spherical PbS particle diameter that this method makes is very big, is 40～50nm (being far longer than 18nm); (X.S.Zhao, I.Gorelikov, S.Musikhin such as Zhao; S.Cauchi, V.Sukhovatkin, E.H.Sargent; E.Kumacheva.Langmuir 2005,21, and 1086.) discover under tensio-active agent 1-sulfydryl USP Kosher (TGL) and dimercapto USP Kosher (DTG) effect; Regulation system pH=11.2 can generate spherical PbS nanocrystal rapidly in a short period of time, but two kinds of tensio-active agents that this method adopts are import reagent; Cost an arm and a leg, be unfavorable for industrial applications.
Summary of the invention
The objective of the invention is to overcome the shortcoming that exists in the prior art, provide that a kind of cost is low, particle diameter is little, the simple water legal system of technology is equipped with PbS ball shaped nano crystalline method.
The object of the invention is realized through following technical proposals:
A kind of water legal system is equipped with PbS ball shaped nano crystalline method; Be to be 2～4 with mol ratio: 10: 1～4: 1～4 cetyl trimethylammonium bromide (CTAB), tert-dodecyl mercaptan, plumbic acetate and sodium sulphite mix also and stir; Reacted 2～24 hours down at 50～150 ℃, produce the black sol solution; Reaction is cooled to room temperature after finishing, spinning, and throw out washs with zero(ppm) water and absolute ethyl alcohol successively, throw out is dried under room temperature naturally again, obtains PbS ball shaped nano crystal.This PbS ball shaped nano crystalline particle diameter is 5～18nm.
The mol ratio of said plumbic acetate and sodium sulphite >=1.
CTAB: tert-dodecyl mercaptan: plumbic acetate: the mol ratio of sodium sulphite is preferably 2～3.5: 10: 3～4: 1～3.
Reflux in the above-mentioned reaction process, wherein temperature of reaction adopts tap water to reflux in the time of 50～100 ℃, and temperature of reaction adopts frozen water to reflux in the time of＞100～150 ℃.
Preferable reaction temperature is 100 ℃, and the reaction times is 8 hours.
The present invention compared with prior art has following advantage and effect:
(1) preparation condition of the present invention is gentle, technology is simple, cost is low, can realize industrialized mass production.
(2) the present invention adopts non-, the cats product compound system that tert-dodecyl mercaptan and CTAB form, and wherein, tert-dodecyl mercaptan plays dual function, is tensio-active agent, is again dispersion agent.These raw materials all are homemade industrial raw material, and are cheap and easy to get, and toxicity is low.
(3) the PbS ball shaped nano crystalline crystal formation for preparing of the present invention is good, the single dispersion, and controllable size, and also particle diameter is less than its Bohr radius (18nm), and quantum effect is obvious.
(4) the PbS ball shaped nano crystal property of the present invention's preparation is stable, and the room temperature held can not produce in 3 months reunites or deposited phenomenon.
Description of drawings
Fig. 1 is the PbS ball shaped nano crystalline XRD figure of the present invention's preparation.
Fig. 2 is the PbS ball shaped nano crystalline TEM figure of the present invention's preparation.
Fig. 3 is the PbS ball shaped nano crystalline electron-diffraction diagram of the present invention's preparation.
Embodiment
Below in conjunction with embodiment the present invention is done further detailed description, but embodiment of the present invention is not limited thereto.
Embodiment 1
In the round-bottomed flask of 100mL, add zero(ppm) water 8mL respectively; 0.1M plumbic acetate solution 4mL; 0.05M CTAB solution 7mL and tert-dodecyl mercaptan 0.25mL (about 1.0mmol); Above solution is mixed and places 50 ℃ of constant temperature oil baths to stir, in the quick injecting reactor of sodium sulfide solution 1mL with 0.1M, stir down and refluxed respectively 2 hours, 8 hours, 16 hours and 24 hours again with tap water.After reaction finishes, to be cooledly carry out spinning to the room temperature (12000rpm, 5min), with zero(ppm) water and absolute ethyl alcohol washing precipitate successively, then with the seasoning at room temperature of resulting throw out, the product that obtains is the chocolate powder.Explain that through X-ray diffraction (XRD) (as shown in Figure 1) and electron diffraction collection of illustrative plates (as shown in Figure 3) product is that PbS is nanocrystalline; It is spherical that transmission electron microscope (TEM) (as shown in Figure 2) is observed the product form, and single the dispersion, particle diameter is between 5～18nm, and along with the prolongation of return time (2～24 hours), the nanocrystalline crystal formation of PbS improves, and size increases.
Embodiment 2
In the round-bottomed flask of 100mL, add zero(ppm) water 10mL respectively; 0.1M plumbic acetate solution 3mL; 0.05M CTAB solution 5mL and tert-dodecyl mercaptan 0.25mL (about 1.0mmol); Above solution is mixed and places 100 ℃ of constant temperature oil baths to stir, in the quick injecting reactor of sodium sulfide solution 2mL with 0.1M, stir down and refluxed respectively 2 hours, 8 hours, 16 hours and 24 hours again with tap water.Pass through the last handling process of example 1 then, obtain the product form with example 1.Along with the prolongation of return time (2～24 hours), the nanocrystalline crystal formation of PbS improves, and size increases.
Embodiment 3
In the round-bottomed flask of 100mL, add zero(ppm) water 10mL respectively; 0.1M plumbic acetate solution 3mL; 0.05M CTAB solution 4mL and tert-dodecyl mercaptan 0.25mL (about 1.0mmol); Above solution is mixed and places 100 ℃ of constant temperature oil baths to stir, in the quick injecting reactor of sodium sulfide solution 3mL with 0.1M, stir down and refluxed respectively 2 hours, 8 hours, 16 hours and 24 hours again with tap water.Pass through the last handling process of example 1 then, obtain the product form with example 1.Along with the prolongation of return time (2～24 hours), the nanocrystalline crystal formation of PbS improves, and size increases.
Embodiment 4
In the round-bottomed flask of 100mL, add zero(ppm) water 8mL respectively; 0.1M plumbic acetate solution 4mL; 0.05M CTAB solution 7mL and tert-dodecyl mercaptan 0.25mL (about 1.0mmol); Mix above solution and place 120 ℃ of constant temperature oil baths to stir, in the quick injecting reactor of sodium sulfide solution 1mL with 0.1M, stir down and refluxed respectively 2 hours, 8 hours, 16 hours and 24 hours again with frozen water.Pass through the last handling process of example 1 then, obtain the product form with example 1.Along with the prolongation of return time (2～24 hours), the nanocrystalline crystal formation of PbS improves, and size increases.
Embodiment 5
In the round-bottomed flask of 100mL, add zero(ppm) water 10mL respectively; 0.1M plumbic acetate solution 3mL; 0.05M CTAB solution 5mL and tert-dodecyl mercaptan 0.25mL (about 1.0mmol); Mix above solution and place 150 ℃ of constant temperature oil baths to stir, in the quick injecting reactor of sodium sulfide solution 2mL with 0.1M, stir down and refluxed respectively 2 hours, 8 hours, 16 hours and 24 hours again with frozen water.Pass through the last handling process of example 1 then, obtain the product form with example 1.Along with the prolongation of return time (2～24 hours), the nanocrystalline crystal formation of PbS improves, and size increases.
Embodiment 6.
In the round-bottomed flask of 100mL, add 11mLH
2O; The plumbic acetate solution of 4mL 0.1M; 4mL0.05M CTAB solution and 0.25mL tert-dodecyl mercaptan (about 1.0mmol); Above solution is mixed and places 100 ℃ of constant temperature oil baths to stir, in the quick injecting reactor of sodium sulfide solution 1mL with 0.1M, stir down and refluxed 8 hours again with tap water.Pass through the last handling process of example 1 then, obtain the product form with example 1.The nanocrystalline crystal formation of PbS is good, and single the dispersion, particle diameter is 8～10nm.
Claims (5)
1. a water legal system is equipped with PbS ball shaped nano crystalline method; It is characterized in that: with mol ratio is 2～4: 10: 1～4: 1～4 cetyl trimethylammonium bromide, tert-dodecyl mercaptan, plumbic acetate and sodium sulphite mix and stir; Reacted 2～24 hours down at 50～150 ℃, produce the black sol solution; Reaction is cooled to room temperature after finishing, spinning, and throw out washs with zero(ppm) water and absolute ethyl alcohol successively, throw out is dried under room temperature naturally again, obtains PbS ball shaped nano crystal.
2. water legal system according to claim 1 is equipped with PbS ball shaped nano crystalline method, it is characterized in that: the mol ratio of said plumbic acetate and sodium sulphite >=1.
3. water legal system according to claim 1 is equipped with PbS ball shaped nano crystalline method, it is characterized in that: cetyl trimethylammonium bromide: tert-dodecyl mercaptan: plumbic acetate: the mol ratio of sodium sulphite is 2～3.5: 10: 3～4: 1～3.
4. water legal system according to claim 1 is equipped with PbS ball shaped nano crystalline method; It is characterized in that: reflux in the said reaction process; Wherein temperature of reaction adopts tap water to reflux in the time of 50～100 ℃, and temperature of reaction is greater than 100 ℃ and adopt frozen water to reflux during smaller or equal to 150 ℃.
5. water legal system according to claim 1 is equipped with PbS ball shaped nano crystalline method, it is characterized in that: temperature of reaction is 100 ℃, and the reaction times is 8 hours.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101049960A (en) * | 2007-03-29 | 2007-10-10 | 浙江大学 | Method for fabricating Nano rod of lead sulfide |
| CN101402466A (en) * | 2008-10-28 | 2009-04-08 | 杭州电子科技大学 | Method for producing monodisperse cube shaped pulmbous sulfide nanocrystalline |
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| CN101049960A (en) * | 2007-03-29 | 2007-10-10 | 浙江大学 | Method for fabricating Nano rod of lead sulfide |
| CN101402466A (en) * | 2008-10-28 | 2009-04-08 | 杭州电子科技大学 | Method for producing monodisperse cube shaped pulmbous sulfide nanocrystalline |
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| JP特开2008-56511A 2008.03.13 |
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