CN100395187C - Prepn process of nanometer hollow IIB sulfide ball - Google Patents

Prepn process of nanometer hollow IIB sulfide ball Download PDF

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CN100395187C
CN100395187C CNB2006101170715A CN200610117071A CN100395187C CN 100395187 C CN100395187 C CN 100395187C CN B2006101170715 A CNB2006101170715 A CN B2006101170715A CN 200610117071 A CN200610117071 A CN 200610117071A CN 100395187 C CN100395187 C CN 100395187C
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solution
iib
preparation
sulfide nano
product
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CN1931726A (en
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吴庆生
段树敏
贾润萍
孙冬梅
丁亚平
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Tongji University
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Tongji University
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Abstract

The present invention belongs to the field of inorganic nanometer material technology, and is especially preparation process of nanometer hollow IIB sulfide ball. The preparation process includes the following steps: taking fresh egg membrane, washing, air drying, soaking in mixed chloroform/phenanthroline solution to obtain supporting liquid film; compounding solution A and solution B of concentration 0.10-0.40 mol/L in the same molar concentration ratio separately; setting solution A and solution B separately on two sides of the supporting liquid film for still reaction for 36-60 hr; taking the solution with precipitate, centrifugally separating, and washing to obtain the required product. The present invention provides one way for controlled synthesis of nanometer material.

Description

A kind of preparation method of II B sulfide nano-material
Technical field
The invention belongs to technical field of inorganic nanometer material, be specifically related to a kind of preparation method of IIB sulfide nano-material.
Background technology
Nano-hollow ball is because its unique structure, optics and surface properties have caused extensive studies interest, and the material of this structure can be used for different aspects such as drug delivery, chemical storage, photoelectronics, katalysis.IIB sulfide is as the important semiconductor material of gang, because its potential using value receives much attention.
Yet, because the sulfide pattern is wayward.Up to now, the preparation method of IIB sulfide nano-material employing is generally template.There is complicated operation in template, and product washs difficulty at last, many shortcomings such as preparation process trouble.Therefore develop a kind of modern design, the method for preparing IIB sulfide nano-hollow material convenient and simple, with low cost, that reaction conditions is gentle is significant.
Summary of the invention
The object of the present invention is to provide a kind of with low cost, reaction conditions is gentle, can production structure the preparation method of IIB sulfide nano-material of novelty.
The preparation method of the IIB sulfide nano-material that the present invention proposes, its concrete steps are as follows:
(1) gets fresh egg membrane, clean (as adopting washing such as distilled water), dry, place the mixing solutions of chloroform/phenanthroline to soak 12-30 hour, make immobilized liquid membrane; Add 0.05-0.2 gram chloroform in wherein per 40 milliliters of phenanthrolines;
(2) prepare solution A and the solution B that volumetric molar concentration is 0.10-0.40mol/L respectively, the molar concentration rate of solution A and solution B is 1: 1, solution A, solution B are placed the immobilized liquid membrane both sides of step (1) gained respectively, standing and reacting 36-60 hour, taking out wherein, a side contains sedimentary solution, centrifugation, washing promptly gets desired product;
Wherein, described solution A is ZnCl 2Solution, HgCl 2Solution, CdSO 4Solution, Cd (NO 3) 2Solution or CdCl 2In the solution etc. any, described solution B is Na 2S solution or K 2In the S solution etc. any.
Among the present invention, soak time is 18-26 hour described in the step (1).
Among the present invention, add in citric acid, nitrilotriacetic acid(NTA), EDTA or the quadrol etc. any in the step (2) in solution B, add-on is the 0.5%-4% of B liquor capacity.
Among the present invention, time of repose is 40-50 hour described in the step (2).
Among the present invention, washing described in the step (2) can adopt distilled water, acetone and dehydrated alcohol to clean 3-6 time successively.
Products therefrom of the present invention can characterize by transmission electron microscope (TEM) or x-ray powder diffraction instrument (XRD).
Reaction mechanism of the present invention is: according to the inductive effect of transmission of the selectivity of carrier in the liquid film and organism structure, and the two mutual not curved interface of the alternate formation of infiltrate are template, and promptly transmission-template-abduction mechanism is controlled the formation of nano material.
The present invention has following advantage:
1, because the present invention chooses redistilled water as reaction media in preparation process, because of its wide material sources, therefore low price makes production cost of the present invention very cheap.
2, because the present invention adopts the immobilized liquid membrane system, wherein the organic solvent and the aqueous solution do not soak into mutually and are forming curved surface at the interface, for the formation of product provides structural framing, added that bioactive supporter has the control action kou of inducing again, the product that the present invention is made has the hollow structure of anticipation, for the exploitation of functional materials is had laid a good foundation.
3, because the present invention only need adjust kind and concentration, additive, temperature of reaction and the reaction times etc. of reactant, can synthesize the IIB sulfide nano-material of different-shape, the gained nano material is of a size of 10 nanometers-180 nanometer.Therefore have easy to operate, technology and simple, the free of contamination advantage of equipment, productive rate is up to 90%.
4, the product of the present invention's preparation has performances such as good light, electricity, absorption peak blue shift.
5, raw material of the present invention is easy to get, and is with low cost, simple to operate, and plant and instrument is easy, product appearance structure novelty, and the purity height, it is convenient to handle, and is easy to industrialization, and new approach and thinking is provided for the control of nano material is synthetic.
Description of drawings
Fig. 1 is the shape appearance figure that the transmission electron microscope (TEM) of the embodiment of the invention 1 products therefrom obtains.
Fig. 2 is the shape appearance figure that the transmission electron microscope (TEM) of the embodiment of the invention 2 products therefroms obtains.
Fig. 3 is the shape appearance figure that the transmission electron microscope (TEM) of the embodiment of the invention 3 products therefroms obtains.
Embodiment
Further specify the present invention below by embodiment.
Embodiment 1
(1) get fresh egg membrane, clean with distilled water wash, dry, place the mixing solutions of chloroform/phenanthroline to soak 30 hours, make immobilized liquid membrane; Add 0.1 gram chloroform in wherein per 40 milliliters of phenanthrolines;
(2) prepare the ZnCl that volumetric molar concentration is 0.20mol/L respectively 2Solution and Na 2S solution is wherein at Na 2The citric acid that adds 1% (volume percent) in the S solution.Again solution A and solution B being placed the immobilized liquid membrane of step (1) gained respectively is the and arranged on left and right sides of egg film, standing and reacting 2 days, take out a side and contain sedimentary solution, carry out centrifugation, the precipitated product that obtains respectively cleans 3 times with distilled water, acetone and dehydrated alcohol successively, can obtain desired product ZnS.
Products obtained therefrom is stored in the dehydrated alcohol, with XRD or TEM the structure and the pattern of product is characterized respectively, as can be seen, this product is pure from the TEM shape appearance figure of Fig. 1, is the mixture of hollow ball and nanoparticle, and the diameter of product is about 10 nanometers.
Embodiment 2
Prepare the CdSO that molar solution is 0.20mol/L respectively 4And Na 2S solution is wherein at Na 2The citric acid that adds 1% (volume percent) in the S solution.Other conditions and step and embodiment 1 are identical.Products obtained therefrom CdS is stored in the dehydrated alcohol, with XRD and TEM the structure and the pattern of product is characterized respectively, as can be seen from Figure 2, the product diameter that obtains is the hollow ball of 30-50 nanometer, and the crystallographic system of product is identical with embodiment 1.The product purity height.Compare with embodiment 1, the blue shift degree of fluorescence peak is bigger.
Embodiment 3
Prepare the HgCl that volumetric molar concentration is 0.15mol/L respectively 2Solution and Na 2S solution is wherein at Na 2The citric acid that adds 1% (volume percent) in the S solution.Other conditions and step and embodiment 1 are identical, and HgS is stored in the dehydrated alcohol with products obtained therefrom.With XRD and TEM the structure and the pattern of product are characterized respectively, as can be seen from Figure 3, the product diameter that obtains is about the hollow ball of 150 nanometers, and the crystallographic system of product is identical with embodiment 1.The product purity height.Compare with embodiment 1, the blue shift degree of fluorescence peak is bigger.
Embodiment 4
Prepare the CdSO that volumetric molar concentration is 0.20mol/L respectively 4And K 2S solution is at K 2The quadrol that adds 1% (volume percent) in the S solution.Other conditions and step and embodiment 1 are identical.The product C dS that obtains is that diameter is the particle about 10 nanometers, and the crystallographic system of product is identical with embodiment 2.The product purity height.Compare with embodiment 2, the blue shift degree of fluorescence peak is less.
Embodiment 5
Prepare the CdSO that volumetric molar concentration is 0.20mol/L respectively 4And Na 2S solution is directly used in the reaction system barrier film with the fresh-laid egg film, and not doping, and other conditions and step and embodiment 1 are identical, and the product that obtains is the about 10 nano-tube/CdS solid sphere chains of diameter, and the crystallographic system of product is identical with embodiment 1.The product purity height, optical property is good.Compare with embodiment 1, the blue shift degree of fluorescence peak is bigger.
Embodiment 6
Prepare the CdSO that molar solution is 0.20mol/L respectively 4And Na 2S solution is wherein at Na 2The citric acid of adding 4% in the S solution.Other conditions and step and embodiment 1 are identical.The product that obtains is the about 100 nano-tube/CdS nano hollow balls of diameter, and is identical with embodiment 2.The product purity height, optical property is basic similar to embodiment 1.
Embodiment 7
Prepare the CdSO that molar solution is 0.20mol/L respectively 4And Na 2S solution, two reactants directly mix, and without any additive, the product C dS that obtains is cotton-shaped aggregate, and the crystallographic system of product is identical with embodiment 1.The product purity height, optical property is good.Compare with embodiment 1, its fluorescence peak position tangible blue shift do not occur with respect to conventional material.
Embodiment 8
(1) get fresh egg membrane, clean with distilled water wash, dry, place the mixing solutions of chloroform/phenanthroline to soak 30 hours, make immobilized liquid membrane; Add 0.2 gram chloroform in wherein per 40 milliliters of phenanthrolines;
(2) prepare the Cd (NO that volumetric molar concentration is 0.40mol/L respectively 3) 2Solution and K 2S solution is wherein at K 2The nitrilotriacetic acid(NTA) that adds 3% (volume percent) in the S solution is with Cd (NO 3) 2Solution and K 2S solution places the immobilized liquid membrane both sides of step (1) gained respectively, standing and reacting 36 hours, and a taking-up wherein side contains sedimentary solution, and centrifugation is cleaned 5-6 time successively with distilled water, acetone and dehydrated alcohol, promptly gets desired product CdS.
The product that obtains is the particle of diameter 50-80 nanometer, and the crystallographic system of product is identical with embodiment 1.The product purity height, optical property is good.Compare with embodiment 1, its fluorescence peak position tangible blue shift occurs with respect to conventional material.
Embodiment 9
(1) get fresh egg membrane, clean with distilled water wash, dry, place the mixing solutions of chloroform/phenanthroline to soak 18 hours, make immobilized liquid membrane; Add 0.15 gram chloroform in wherein per 40 milliliters of phenanthrolines;
(2) prepare the CdSO that volumetric molar concentration is 0.30mol/L respectively 4Solution and K 2S solution is wherein at K 2The EDTA of adding 2% in the S solution is with CdSO 4Solution and K 2S solution places the immobilized liquid membrane both sides of step (1) gained respectively, standing and reacting 40 hours, and a taking-up wherein side contains sedimentary solution, and centrifugation is alternately cleaned 4-5 time with distilled water, acetone and dehydrated alcohol, promptly gets desired product CdS.
The product that obtains is the hollow ball of diameter 50-80 nanometer, and the crystallographic system of product is identical with embodiment 1.The product purity height, optical property is good.Compare with embodiment 1, its fluorescence peak position tangible blue shift occurs with respect to conventional material.
Embodiment 10
(1) get fresh egg membrane, clean with distilled water wash, dry, place the mixing solutions of chloroform/phenanthroline to soak 26 hours, make immobilized liquid membrane; Add 0.05 gram chloroform in wherein per 40 milliliters of phenanthrolines;
(2) prepare the HgCl that volumetric molar concentration is 0.10mol/L respectively 2Solution and K 2S solution is wherein at K 2The citric acid of adding 2.5% in the S solution is with CdSO 4Solution and K 2S solution places the immobilized liquid membrane both sides of step (1) gained respectively, standing and reacting 40 hours, and a taking-up wherein side contains sedimentary solution, and centrifugation is cleaned 3-4 time successively with distilled water, acetone and dehydrated alcohol, promptly gets desired product CdS.
The product that obtains is the hollow ball of diameter 150-180 nanometer, and the crystallographic system of product is identical with embodiment 1.The product purity height, optical property is good.Compare with embodiment 1, its fluorescence peak position tangible blue shift occurs with respect to conventional material.

Claims (6)

1. the preparation method of an IIB sulfide nano-material is characterized in that concrete steps are as follows:
(1) gets fresh egg membrane, clean, dry, place the mixing solutions of chloroform/phenanthroline to soak 12-30 hour, make immobilized liquid membrane; Add 0.05-0.2 gram chloroform in wherein per 40 milliliters of phenanthrolines;
(2) prepare solution A and the solution B that volumetric molar concentration is 0.10-0.40mol/L respectively, the molar concentration rate of solution A and solution B is 1: 1, solution A, solution B are placed the immobilized liquid membrane both sides of step (1) gained respectively, standing and reacting 36-60 hour, taking out wherein, a side contains sedimentary solution, centrifugation, washing promptly gets desired product;
Wherein, described solution A is ZnCl 2Solution, HgCl 2Solution, CdSO 4Solution, Cd (NO 3) 2Solution or CdCl 2In the solution any, described solution B is Na 2S solution or K 2In the S solution any.
2. according to the preparation method of the described IIB sulfide nano-material of claim 1, it is characterized in that soak time is 18-26 hour described in the step (1).
3. according to the preparation method of the described IIB sulfide nano-material of claim 1, it is characterized in that in solution B, adding in the step (2) in citric acid, nitrilotriacetic acid(NTA), EDTA or the quadrol any, add-on is the 0.5%-4% of B liquor capacity.
4. according to the preparation method of the described IIB sulfide nano-material of claim 1, it is characterized in that time of repose is 40-50 hour described in the step (2).
5. according to the preparation method of the described IIB sulfide nano-material of claim 1, it is characterized in that the employing of washing described in the step (2) distilled water, acetone and dehydrated alcohol clean 3-6 time successively.
6. according to the preparation method of the described IIB sulfide nano-material of claim 1, it is characterized in that products therefrom is that TEM or x-ray powder diffraction instrument are that XRD characterizes by transmission electron microscope.
CNB2006101170715A 2006-10-12 2006-10-12 Prepn process of nanometer hollow IIB sulfide ball Expired - Fee Related CN100395187C (en)

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CN101058437B (en) * 2007-04-10 2010-10-06 安徽大学 Liquid state preparation method for nano cadmium sulfide hollow sphere
CN107814415B (en) * 2016-09-13 2019-07-05 同济大学 The hydro-thermal supported liquid membrane synthetic method of nano material
CN114873642B (en) * 2022-04-06 2023-05-16 同济大学 Doughnut-shaped strontium molybdate nano material and preparation method thereof

Citations (3)

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Publication number Priority date Publication date Assignee Title
WO2000050341A1 (en) * 1999-02-23 2000-08-31 Hw Process Technologies, Inc. Method of acid concentration following biological oxidative generation of sulfuric acid from sulfides
CN1522794A (en) * 2003-09-05 2004-08-25 同济大学 Bionic nano superstructure material preparation method using white envelope as model
CN1719578A (en) * 2005-04-29 2006-01-11 同济大学 A kind of method for preparing IIB family semiconductor sulfuration thing nano material

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2000050341A1 (en) * 1999-02-23 2000-08-31 Hw Process Technologies, Inc. Method of acid concentration following biological oxidative generation of sulfuric acid from sulfides
CN1522794A (en) * 2003-09-05 2004-08-25 同济大学 Bionic nano superstructure material preparation method using white envelope as model
CN1719578A (en) * 2005-04-29 2006-01-11 同济大学 A kind of method for preparing IIB family semiconductor sulfuration thing nano material

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
半导体硫化银纳米管的制备与光学性能. 杨小红，吴庆生，丁亚平，张国欣.稀有金属材料与工程，第35卷第6期. 2006 *
银、铜硫化物纳米球的活性模板合成极其光学性能研究. 刘金库，吴庆生，丁亚平，余意.功能材料，第35卷第6期. 2004 *

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