CN103803636B - Preparation method of zinc sulfide nuclear hollow microspheres - Google Patents
Preparation method of zinc sulfide nuclear hollow microspheres Download PDFInfo
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- CN103803636B CN103803636B CN201210455975.4A CN201210455975A CN103803636B CN 103803636 B CN103803636 B CN 103803636B CN 201210455975 A CN201210455975 A CN 201210455975A CN 103803636 B CN103803636 B CN 103803636B
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Abstract
The invention discloses a preparation method of zinc sulfide nuclear hollow microspheres. The preparation method is characterized by comprising the following steps: (1) dosing: dissolving a phenylamine monomer in an organic solvent insoluble in water to obtain a solution A for use; sequentially dissolving a zinc-containing compound, strong base and a sulfur-containing compound in deionized water to obtain a solution B; adding the prepared persulfate aqueous solution into the solution B to obtain a solution C; and finally, adding the solution C into the solution A to obtain a insoluble two-phase mixed solution with a clear interface; (2) standing at constant temperature and reacting for 12-24 at room temperature, wherein slight yellow precipitate appears on the two-phase interface; (3) washing; and (4) drying to obtain the ZnS nuclear hollow microspheres. The method is simple and easy to implement, and the morphological control over the synthetic material is stable. The obtained product can be applied to the fields such as secondary battery materials, photovoltaic devices, photocatalysts and gas sensors.
Description
Technical field
The present invention relates to a kind of preparation method with core tiny balloon, particularly relate to a kind of interfacial synthesis method of zinc sulphide band core tiny balloon, belong to material chemistry technical field.
Background technology
ZnS is a kind of II-VI group semiconductor compound of broad-band gap, has excellent optical, electrical, thermal properties, is widely used in fields such as optics, photovoltaic device, energy storage device, photocatalyst, gas sensors.The synthesis of different-shape ZnS nanostructure is the focus of research always, and the synthesis of the nanometer ball of various ZnS, nanometer rod, nanotube has report.ZnS tiny balloon causes people's extensive concern due to its special structure and surface properties.There are reports in the synthesis of ZnS tiny balloon, as utilized carbon ball, silicon ball as hard template, or utilize polyoxyethylene glycol, polyvinylpyrrolidone, P123 etc. as the hot method synthesis of soft template hydrothermal/solvent, but these methods need high pressure resistant steel still and higher temperature, technique relative complex.The normal temperature and pressure synthesis of ZnS tiny balloon rarely has report at present.
Compared with simple tiny balloon, the tiny balloon with removable kernel effectively can be optimized the performance of material in catalysis, stored energy, sensing etc. or realize more complicated multifunctionality.Band core its shell of tiny balloon and kernel can be of the same race or foreign materials, and existing technology one adopts template stepwise synthesis, and namely the technique of " inner nuclear material synthesis mould material coated sheating material coated die plate corrosion cleaning ", has reported SiO
2-SiO
2, Au-ZrO
2, the multiple band core hollow structure such as Pt-C synthesizes in this way, the method needs substep independent operation usually, synthesizes relative with cleaning tediously long.Second method utilizes " Kirkendall effect " or " Ostwald slaking " to synthesize, and the people such as B. Liu report and utilize Ostwald slaking mechanism growing ZnS band core tiny balloon (B. Liu, H. C. Zeng, Small 2005,1,566).Compared with template separate operations, the method operation steps is relatively less, still uses high-temperature solvent thermal response (180 technically
oc) and need longer time (>52h), current nucleocapsid homogeneity ZnS is with the synthesis of the normal temperature and pressure of core tiny balloon also not to report.
Summary of the invention
For the deficiencies in the prior art, the invention provides a kind of simple and feasible interfacial synthesis method method, under normal temperature and pressure, utilize synthesis ZnS to be with core tiny balloon.
A preparation method for zinc sulphide band core tiny balloon, is characterized in that, comprise the following steps:
(1) prepare burden: first aniline monomer is dissolved in that to obtain solution A in the organic solvent not molten mutually with water for subsequent use, again the compound containing the compound of zinc, highly basic and sulfur-bearing is dissolved in deionized water successively and obtains solution B, then prepare the persulphate aqueous solution to add in solution B and obtain solution C, finally solution C is added in solution A and obtained the mutual exclusive two-phase mixtures liquid in clear interface;
(2) constant temperature standing and reacting 12 ~ 24 hours under room temperature, there is pale yellow precipitate in two-phase interface;
(3) wash;
(4) dry.
The described organic solvent not molten mutually with water is chloroform or tetracol phenixin or methylene dichloride, and aniline concentration is in organic solvent 0.1 ~ 0.4 molL
-1.
The compound of described zinc is one in zinc nitrate, zinc chloride, zinc acetate or its combination, and the concentration in solution B is 0.1 ~ 0.5 molL
-1; Described highly basic is one in sodium hydroxide, potassium hydroxide or its combination, and the concentration in solution B is 2 ~ 4 molL
-1; The compound of described sulfur-bearing is thiocarbamide, or thioacetamide, or Sulfothiorine, and the Compound Phase adding molar weight and zinc is same; Described persulphate is one in Sodium Persulfate, Potassium Persulphate, ammonium persulphate or its combination, and the concentration of the described persulphate aqueous solution is 0.1 ~ 0.4 molL
-1.
Described washing is the pale yellow precipitate for obtaining, with the alternately washing of ethanol, tetrahydrofuran (THF) and deionized water, whizzer precipitation or pumping and filtering device is adopted to filter after each washing, filtration product is disperseed again in deionized water or ethanol, repeatedly filter until filtrate pH value is 7, last washing with alcohol is with convenient and dry.
Described drying is the nano-powder for obtaining, and is placed in the vacuum drying oven of 50 ~ 70 DEG C and dries, vacuum tightness <133Pa.
The present invention to utilize on interface the synchronous polyaniline (PANi) generated directly to generate ZnS/PANi/ZnS three-decker for intermediate die plate and ZnS in the solution with template PANi synthesis speed difference, obtains ZnS band core tiny balloon with tetrahydrofuran (THF) after washing away PANi.Compared with the method for conventional synthesis band core hollow ball, the method step obviously reduces, and synthesis condition is gentle, and method is simple, and the morphology control of synthetic materials is stablized.Products therefrom can be applicable to the fields such as secondary battery material, photovoltaic device, photocatalyst, gas sensor.
Accompanying drawing explanation
Fig. 1 is the XRD figure spectrum that the embodiment of the present invention 1 synthesizes that ZnS is with core tiny balloon.
Fig. 2 is the field emission scanning electron microscope photo that the embodiment of the present invention 1 synthesizes that ZnS is with core tiny balloon.
Embodiment
Embodiment 1:
First 5 mmol aniline monomers are dissolved in 50 mL tetracol phenixin for subsequent use, then 5 mmol zinc nitrates, 0.1 mol sodium hydroxide and 5 mmol Sulfothiorine are dissolved in 50 mL ionized waters successively obtain solution B, then by 50mL 0.1molL
-1sodium persulfate aqueous solution add in solution B and obtain solution C, finally solution C is added in the carbon tetrachloride solution of aniline and has obtained clear interface mutual exclusive two-phase mixtures liquid (aqueous phase upper oil phase under); Under two-phase mixtures liquid chamber temperature, constant temperature standing and reacting 20 hours, there is pale yellow precipitate in two-phase interface; By the alternately washing of precipitation ethanol, tetrahydrofuran (THF) and deionized water, whizzer precipitation or pumping and filtering device is adopted to filter after each washing, filtration product is disperseed again in deionized water or ethanol, repeatedly filter until filtrate pH value is 7, be placed in the vacuum drying oven of 50 ~ 70 DEG C and dry, obtain ZnS and be with core tiny balloon, productive rate is 87.6%.The XRD figure spectrum of product is as shown in Figure 1, well corresponding with ZnS standard diagram (JCPDS Card 05-0566); Transmission electron microscope photo as shown in Figure 2, hollow ball size about 1 ~ 2 micron, wall thickness about 50 ~ 80 nanometer, kernel about 400 ~ 650 nanometer.
Embodiment 2:
Repeat embodiment 1, but replace zinc nitrate and Sulfothiorine with zinc chloride and thiocarbamide respectively, obtain ZnS and be with core tiny balloon, productive rate is 84.3%.
Embodiment 3:
Repeat embodiment 1, but replace zinc nitrate and Sulfothiorine with zinc acetate and thioacetamide respectively, obtain ZnS and be with core tiny balloon, productive rate is 91.2%.
Embodiment 4,5:
Repeat embodiment 1, but replace tetracol phenixin with chloroform, phosgene respectively, obtain ZnS and be with core tiny balloon, productive rate is respectively 88.1% and 86.1%.
Above-mentioned is can understand and apply the invention for ease of those skilled in the art to the description of embodiment.Person skilled in the art obviously easily can make various amendment to these embodiments, and General Principle described herein is applied in other embodiment and need not through performing creative labour.Therefore, the invention is not restricted to embodiment here, those skilled in the art are according to announcement of the present invention, and the improvement made for the present invention and amendment all should within protection scope of the present invention.
Claims (4)
1. a preparation method for zinc sulphide band core tiny balloon, is characterized in that, comprise the following steps:
(1) prepare burden: first aniline monomer is dissolved in that to obtain solution A in the organic solvent not molten mutually with water for subsequent use, again the compound containing the compound of zinc, highly basic and sulfur-bearing is dissolved in deionized water successively and obtains solution B, then prepare the persulphate aqueous solution to add in solution B and obtain solution C, finally solution C is added in solution A and obtain the immiscible two-phase mixtures liquid in clear interface;
(2) constant temperature standing and reacting 12 ~ 24 hours under room temperature, there is pale yellow precipitate in two-phase interface;
(3) wash; Described washing is the pale yellow precipitate for obtaining, with the alternately washing of ethanol, tetrahydrofuran (THF) and deionized water, whizzer precipitation or pumping and filtering device is adopted to filter after each washing, filtration product is disperseed again in deionized water or ethanol, repeatedly filter until filtrate pH value is 7, last washing with alcohol is with convenient and dry;
(4) dry.
2. the preparation method of a kind of zinc sulphide band core tiny balloon according to claim 1, is characterized in that, the described organic solvent not molten mutually with water is chloroform or tetracol phenixin or methylene dichloride, and aniline concentration is in organic solvent 0.1 ~ 0.4 molL
-1.
3. the preparation method of a kind of zinc sulphide band core tiny balloon according to claim 1, is characterized in that, the compound of described zinc is one in zinc nitrate, zinc chloride, zinc acetate or its combination, and the concentration in solution B is 0.1 ~ 0.5 molL
-1; Described highly basic is one in sodium hydroxide, potassium hydroxide or its combination, and the concentration in solution B is 2 ~ 4 molL
-1; The compound of described sulfur-bearing is thiocarbamide, or thioacetamide, or Sulfothiorine, and the Compound Phase adding molar weight and zinc is same; Described persulphate is one in Sodium Persulfate, Potassium Persulphate, ammonium persulphate or its combination, and the concentration of the described persulphate aqueous solution is 0.1 ~ 0.4 molL
-1.
4. the preparation method of a kind of zinc sulphide band core tiny balloon according to claim 1, it is characterized in that, described drying is the nano-powder for obtaining, and is placed in the vacuum drying oven of 50 ~ 70 DEG C and dries, vacuum tightness <133Pa.
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| CN103803636B true CN103803636B (en) | 2015-04-22 |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101259402A (en) * | 2004-11-11 | 2008-09-10 | 中国科学院化学研究所 | Method for preparing hollow ball with double-layer structure and hollow ball with multi-layer complex structure by template method |
| CN101486487A (en) * | 2008-01-16 | 2009-07-22 | 中国科学院合肥物质科学研究院 | Zinc sulfide micron hollow sphere and preparation method thereof |
| CN101519223A (en) * | 2009-04-10 | 2009-09-02 | 武汉理工大学 | One-step template-free method for preparing a great amount of monodisperse ZnS hollow nanospheres |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101259402A (en) * | 2004-11-11 | 2008-09-10 | 中国科学院化学研究所 | Method for preparing hollow ball with double-layer structure and hollow ball with multi-layer complex structure by template method |
| CN101486487A (en) * | 2008-01-16 | 2009-07-22 | 中国科学院合肥物质科学研究院 | Zinc sulfide micron hollow sphere and preparation method thereof |
| CN101519223A (en) * | 2009-04-10 | 2009-09-02 | 武汉理工大学 | One-step template-free method for preparing a great amount of monodisperse ZnS hollow nanospheres |
Non-Patent Citations (1)
| Title |
|---|
| Colloidal-route synthesis of N-butylaniline capped ZnS and CdS nanoparticles;Damian C.Onwudiwe et al.;《Materials Letters》;20121023;第92卷;第71-74页 * |
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