CN101177551A - Method for preparing silica modified zinc sulfide nano material - Google Patents
Method for preparing silica modified zinc sulfide nano material Download PDFInfo
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- CN101177551A CN101177551A CNA2007100505222A CN200710050522A CN101177551A CN 101177551 A CN101177551 A CN 101177551A CN A2007100505222 A CNA2007100505222 A CN A2007100505222A CN 200710050522 A CN200710050522 A CN 200710050522A CN 101177551 A CN101177551 A CN 101177551A
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Abstract
The invention relates to a preparation method of silica-modified zinc sulphide nanometer material, in particular to a preparation method of zinc sulphide nanometer material, belonging to technical field of the inorganic chemical materials. Zinc acetate is adopted as the zinc source, sodium silicate or tetra ethyl ortho silicate are adopted as the silica source, sodium sulphide is adopted as the sulfur source, and the reaction process of colloidal sol, gel, and hydrothermal crystallization are adopted to prepare the silica-modified zinc sulphide nanometer material. The silica in the prepared silica-modified zinc sulphide nanometer material is mainly clad on the surface of the zinc sulphide. The preparation method of the invention has the advantages of simplicity, easy operation, and suitability for large-scale production. The prepared silica-modified zinc sulphide nanometer material has the advantages of uniform granules, good stability and monodispersity, thus the product can be used for fluorescer, photoelectric devices and other fields.
Description
Technical field
The invention belongs to the inolrganic chemicals technical field, be specifically related to the preparation method of zinc sulfide nano-material.
Background technology
Zinc sulfide nano-material has special photoelectric property, is with a wide range of applications in fields such as luminescent material, optoelectronic equipment and LED material.The application performance of zinc sulfide nano-material is decided by its particle diameter and Surface Physical Chemistry character.Usually, the physicochemical property of zinc sulfide nano-material are very unstable, change easily in application, and it is very important therefore controlling its particle diameter and improving its stability.The method of control zinc sulfide nano-material particle diameter commonly used at present and its stability of raising is to adopt other materials to carry out the surface to coat.Coating commonly used has organic polymer and inorganic polymer (comprising silicon oxide and pottery etc.), coats back and nano particle and forms nanocomposite structures.Wherein the zinc sulfide nano mixture of silicon oxide coated modification demonstrates more and more important application prospects on modern times demonstration and luminescence technology.But the inorganic coating of zinc sulphide at present mainly is to adopt sol-gel method or laser deposition to be embedded in silica glass or the film, and cost is higher, operation inconvenience, so it has been subjected to very big restriction in Application Areas, and be unfavorable for scale operation.
Summary of the invention
The invention provides a kind of preparation method of silica modified zinc sulfide nano-material, this method is simple to operate, with low cost, is suitable for scale operation.Even according to the silica modified zinc sulfide nano-material particle diameter that the present invention is prepared, and have good thermostability and monodispersity.
The present invention is the zinc source with the zinc acetate, is the silicon source with water glass or tetraethoxy, is the sulphur source with sodium sulphite, adopts sol-gel-hydro-thermal reaction crystallization process to prepare silica modified zinc sulfide nano-material.
Detailed technology scheme of the present invention is as follows:
A kind of preparation method of silica modified zinc sulfide nano-material may further comprise the steps:
Step 1. preparation silicon oxide water-sol A.
Secure ph is 1.0～3.0 aqueous hydrochloric acid, adds the silicon source down at 40～50 ℃ then, stirs until complete hydrolysis, gets silicon oxide water-sol A, and is stand-by.
Zinc acetate is dissolved in the water, is mixed with 0.1～0.5molL
-1Zinc acetate aqueous solution B, add ethylenediamine tetraacetic acid (EDTA) (EDTA) then and stir, be 5.5～6.8 with ammoniacal liquor regulator solution pH value again, stand-by.
Step 3. formulating vulcanization sodium water solution C.
Sodium sulphite is soluble in water, be mixed with 0.1～0.5molL
-1Sodium sulfide solution C, stand-by.
Step 4. preparation zinc sulphide-silica gel.
The zinc acetate aqueous solution B of step 2. gained is added among the silicon oxide water-sol A of step 1. gained, splash into the sodium sulfide solution C of step 3. gained again, make its generation
Zn
2++S
2-→ZnS↓
Abundant reaction, and form zinc sulphide-silica gel D.
The reaction of step 5. hydrothermal crystallizing.
Zinc sulphide-silica gel the D of step 4. gained is transferred in the teflon-lined water heating kettle, the following hydrothermal crystallizing reaction of 120～180 ℃ temperature condition 6～20 hours.
Step 6. aftertreatment.
To filter, dry, grind through the reacted product of step 5. hydrothermal crystallizing, promptly get silica modified zinc sulfide nano-material of the present invention.
Need to prove:
The silicon source of being adopted in the step 1. can be water glass or tetraethoxy.
When in the step 6. product after the hydro-thermal reaction crystallization being dried, temperature is advisable 105～130 ℃ of scopes.Temperature is low excessively, is unfavorable for the rapid removal of moisture content; Decomposition reaction may take place in the too high then zinc sulphide of temperature.
The ethylenediamine tetraacetic acid (EDTA) itself that step 4. adds is not participated in reaction, but can be used for controlling the formation speed of zinc sulphide, plays function of stabilizer; The consumption of ethylenediamine tetraacetic acid (EDTA) preferably and the zinc acetate of step 2. and the sodium sulphite of step 3. be equimolar amount.
Principle of the present invention is to adopt silicon oxide to be coated to the zine sulfide nano particles surface, the effect of playing the growth of control zine sulfide nano particles and improving zns particle stability; Adopt water-heat process to come zine sulfide nano particles is carried out crystallization, avoided the decomposition of the zinc sulphide that the high temperature crystallization causes, prevented the consequence that zine sulfide nano particles is grown up and specific surface area descends that the hard aggregation because of zine sulfide nano particles causes simultaneously.
The present invention compared with prior art has following advantage:
1, preparation method's cost of the present invention is low, reaction process is simple, helps the scale operation of material.
2, the silica modified zinc sulfide nano-material of the present invention's preparation, the X-ray diffraction analysis proof has good zink sulphide crystal formation (as shown in Figure 2), transmission electron microscope proof particle diameter is not more than 50 nanometers (as shown in Figure 3), uniform particles, good dispersity has good thermostability and monodispersity.
3, the silica modified zine sulfide nano particles of the present invention's preparation can be applied in the extensive fields, as fluorescent agent and optoelectronic equipment etc.
Description of drawings
Fig. 1 is a process flow sheet of the present invention.
Fig. 2 is the X-ray diffractogram of the silica modified zine sulfide nano particles of 25% mass ratio of the present invention's preparation.
Fig. 3 is the height explanation transmission electron microscope photo of silica modified zine sulfide nano particles of 25% mass ratio of this preparation.
Embodiment
Embodiment one
In 50ml water, add the 0.5ml tetraethoxy, use 2molL
-1Hydrochloric acid soln to regulate pH value be 2,45 ℃ of stirring hydrolysis down.To regulate liquid pH value with ammoniacal liquor then is 5.5 60ml 0.2molL
-1Zinc acetate aqueous solution add wherein.Under agitation condition, the stablizer ethylenediamine tetraacetic acid (EDTA) of adding and zinc acetate equimolar amount forms white casse liquid.Splash into 60ml 0.2molL then
-1Sodium sulfide solution, stirred solution become slight white casse, continue to stir formation white casse liquid.Then this muddy liquid is transferred in the teflon-lined water heating kettle, 120 ℃ of following hydrothermal crystallizings reacted 20 hours.With sample filtering after the hydro-thermal, wash 3 times, 110 ℃ of oven dry down, grind and promptly get SiO then
2Mass ratio is 10% silica modified zine sulfide nano particles.It is 42 nanometers that electron microscope is observed the silica modified zine sulfide nano particles mean diameter of this kind down, the particle ball-type, evenly, the single dispersion.The XRD measuring result shows that zinc oxide is zink sulphide.
Embodiment two
In 100ml water, add the 1.152g water glass, use 2molL
-1Hydrochloric acid soln to regulate pH value be 2,40 ℃ of stirring hydrolysis down.To regulate liquid pH value with ammoniacal liquor then is 6.0 120ml 0.1molL
-1Zinc acetate aqueous solution add wherein.Under agitation condition, the stablizer ethylenediamine tetraacetic acid (EDTA) of adding and zinc acetate equimolar amount forms white casse liquid.Then with 0.1molL
-1Sodium sulfide solution 120ml splash in the above-mentioned settled solution, stirred solution becomes little white muddiness, continue to stir forms white casse liquid.Then this muddy liquid is transferred in the teflon-lined water heating kettle, 150 ℃ of following hydrothermal crystallizings reacted 12 hours.With sample filtering after the hydro-thermal, wash 3 times, 105 ℃ of oven dry down, grind and promptly get SiO then
2Mass ratio is the zine sulfide nano particles of 25% change silicon modification.It is 35 nanometers that electron microscope is observed the silica modified zine sulfide nano particles mean diameter of this kind down, the particle ball-type, evenly, the single dispersion.The XRD measuring result shows that zinc sulphide is zink sulphide.
Embodiment three
In 50ml water, add the 4.2ml tetraethoxy, use 2molL
-1Hydrochloric acid soln to regulate pH value be 2,50 ℃ of stirring hydrolysis down.To regulate liquid pH value with ammoniacal liquor then is 6.8 60ml 0.2molL
-1Zinc acetate aqueous solution add wherein.Under agitation condition, the stablizer ethylenediamine tetraacetic acid (EDTA) of adding and zinc acetate equimolar amount forms white casse liquid.Jiang 0.2molL then
-1Sodium sulfide solution 60ml splashes in the above-mentioned settled solution, and stirred solution becomes little white muddiness, continues to stir formation white casse liquid.Then this muddy liquid is transferred in the teflon-lined water heating kettle, 180 ℃ of following hydrothermal crystallizings reacted 6 hours.With the sample filtering after the hydro-thermal reaction, wash 3 times, then 130 ℃ of down oven dry, grinding and promptly getting mass ratio is 50% silica modified zine sulfide nano particles.It is 32 nanometers that electron microscope is observed the silica modified zine sulfide nano particles mean diameter of this kind down, the particle ball-type, evenly, the single dispersion.The XRD measuring result shows that zinc sulphide is zink sulphide.
Claims (5)
1. the preparation method of a silica modified zinc sulfide nano-material may further comprise the steps:
Step 1. preparation silicon oxide water-sol A:
Secure ph is 1.0～3.0 aqueous hydrochloric acid, adds the silicon source down at 40～50 ℃ then, stirs until complete hydrolysis, gets silicon oxide water-sol A, and is stand-by;
Step 2. preparation zinc acetate aqueous solution B:
Zinc acetate is dissolved in the water, is mixed with 0.1～0.5molL
-1Zinc acetate aqueous solution B, add ethylenediamine tetraacetic acid (EDTA) then and stir, be 5.5～6.8 with ammoniacal liquor regulator solution pH value again, stand-by;
Step 3. formulating vulcanization sodium water solution C:
Sodium sulphite is soluble in water, be mixed with 0.1～0.5molL
-1Sodium sulfide solution C, stand-by;
Step 4. preparation zinc sulphide-silica gel:
The zinc acetate aqueous solution B of step 2. gained is added among the silicon oxide water-sol A of step 1. gained, splash into the sodium sulfide solution C of step 3. gained again, make its generation
Zn
2++S
2-→ZnS↓
Abundant reaction, and form zinc sulphide-silica gel D;
The reaction of step 5. hydrothermal crystallizing:
Zinc sulphide-silica gel the D of step 4. gained is transferred in the teflon-lined water heating kettle, the following hydrothermal crystallizing reaction of 120～180 ℃ temperature condition 6～20 hours;
Step 6. aftertreatment:
To filter, dry, grind through the reacted product of step 5. hydrothermal crystallizing, promptly get silica modified zinc sulfide nano-material.
2. the preparation method of silica modified zinc sulfide nano-material according to claim 1 is characterized in that the silicon source of being adopted in the described step 1. is a water glass.
3. the preparation method of silica modified zinc sulfide nano-material according to claim 1 is characterized in that the silicon source of being adopted in the described step 1. is a tetraethoxy.
4. the preparation method of silica modified zinc sulfide nano-material according to claim 1 is characterized in that, when in the described step 6. the reacted product of hydrothermal crystallizing being dried, temperature is 105～130 ℃ of scopes.
5. the preparation method of silica modified zinc sulfide nano-material according to claim 1 is characterized in that, the consumption of the ethylenediamine tetraacetic acid (EDTA) that described step 4. adds and the zinc acetate of described step 2. and the sodium sulphite of described step 3. are equimolar amount.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101941677A (en) * | 2010-08-31 | 2011-01-12 | 电子科技大学 | Method for preparing manganese oxide surface modified zinc oxide nano rod |
| CN101402856B (en) * | 2008-11-01 | 2011-07-27 | 中国海洋大学 | Surface finishing method for copper ion doped zinc sulfide nano-material |
| CN101445724B (en) * | 2008-11-04 | 2012-03-21 | 中国海洋大学 | Method for improving surface of zinc sulfide nano-material mixed with copper ion |
| DE102013105794A1 (en) | 2012-06-12 | 2013-12-12 | Sachtleben Chemie Gmbh | Process for the preparation of ZnS particles with a coating of metal oxide containing cobalt, the products thus obtained and their use |
| CN105731521A (en) * | 2016-02-04 | 2016-07-06 | 常州可赛成功塑胶材料有限公司 | Preparation method of indium tin oxide-modified highly-dispersive light-transmitting infrared zinc sulfide |
-
2007
- 2007-11-15 CN CNB2007100505222A patent/CN100567411C/en not_active Expired - Fee Related
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101402856B (en) * | 2008-11-01 | 2011-07-27 | 中国海洋大学 | Surface finishing method for copper ion doped zinc sulfide nano-material |
| CN101445724B (en) * | 2008-11-04 | 2012-03-21 | 中国海洋大学 | Method for improving surface of zinc sulfide nano-material mixed with copper ion |
| CN101941677A (en) * | 2010-08-31 | 2011-01-12 | 电子科技大学 | Method for preparing manganese oxide surface modified zinc oxide nano rod |
| DE102013105794A1 (en) | 2012-06-12 | 2013-12-12 | Sachtleben Chemie Gmbh | Process for the preparation of ZnS particles with a coating of metal oxide containing cobalt, the products thus obtained and their use |
| WO2013185753A1 (en) | 2012-06-12 | 2013-12-19 | Sachtleben Chemie Gmbh | Method for the production of zns particles having a metal oxide coating and a cobalt content, products obtained thereby, and use of said products |
| US9163130B2 (en) | 2012-06-12 | 2015-10-20 | Sachtleben Chemie Gmbh | Method for the production of ZnS particles having a metal oxide coating and a cobalt content, products obtained thereby, and use of said products |
| CN105731521A (en) * | 2016-02-04 | 2016-07-06 | 常州可赛成功塑胶材料有限公司 | Preparation method of indium tin oxide-modified highly-dispersive light-transmitting infrared zinc sulfide |
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| CN100567411C (en) | 2009-12-09 |
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