CN102923759A - Method for preparing pure-phase monodisperse ZnS nanocrystalline by using diethylene glycol serving as solvent - Google Patents
Method for preparing pure-phase monodisperse ZnS nanocrystalline by using diethylene glycol serving as solvent Download PDFInfo
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- CN102923759A CN102923759A CN2012104332295A CN201210433229A CN102923759A CN 102923759 A CN102923759 A CN 102923759A CN 2012104332295 A CN2012104332295 A CN 2012104332295A CN 201210433229 A CN201210433229 A CN 201210433229A CN 102923759 A CN102923759 A CN 102923759A
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Abstract
The invention discloses a method for preparing pure-phase monodisperse ZnS nanocrystalline by using diethylene glycol serving as a solvent. The method comprises steps of dissolving Zn (NO3)2.6H2O in the diethylene glycol, regarding the Zn (NO3)2.6H2O which is dissolved in the diethylene glycol as a zinc source precursor solution, dissolving thiacetamide and Polyvinylpyrrolidone (PVP) in the diethylene glycol, regarding the thiacetamide and the PVP which are dissolved in the diethylene glycol as a sulphur source precursor solution, pouring the sulphur source precursor solution into a flask with three necks which is provided with a condenser tube, feeding a nitrogen flow, heating, injecting the zinc source precursor solution of which the mol ratio of Zn and S is 1:1, conducting reflux for 10 minutes at the temperature from 180 DEG C to 200 DEG C, cooling to the room temperature by using water, cleaning centrifugally by using absolute ethyl alcohol, dispersing zinc oxide nanocrystalline in alcohol and sealing and storing the zinc oxide nanocrystalline. The zinc blende ZnS nanocrystalline which does not have any impure phases and is good in dispersibility is synthesized, the process is free from pollution, the device is simple, the preparation cost is low and the scale industrial production can be applied.
Description
Technical field
The invention relates to nano material, particularly a kind of employing solution chemical method, with Diethylene Glycol as solvent prepare pure phase, monodispersed ZnS is nanocrystalline.
Background technology
Zinc sulphide is with its good optics, electrical properties, opened up the application in its emission on the scene, catalyzer, solar cell, sensor field.As a kind of good photoelectric semiconductor material, ZnS can have different luminous forms, comprises photoluminescence (PL), cathode luminescence (CL), electroluminescent (EL), electrochemiluminescence (ECL), thermoluminescence (TL) etc.Because the grain-size of nanoscale can cause the variation of the various character of material, the nanocrystalline appearance of ZnS also makes it have and good optical property and electrical properties, has further enlarged the widespread use of its every field.
The synthetic aspect of ZnS nano material, mainly use so far microemulsion method or reverse micelle method, chemical Vapor deposition process, hydrothermal method, sluggish precipitation, sol-gel method, pyrolysis method, hot solvent method, template etc. and synthesized the ZnS nano material of various forms, nanocrystalline, the nano-crystal with core-shell structure that comprise zero dimension, the nano wire of one dimension, nano belt, the nanometer sheet of two dimension and structure such as block structure, the Grafting Structure etc. that some are complicated.Maximum problem is to solve its dispersiveness in the process of nano materials, because undersized nano material surface active is higher, reunites together easily.Up to the present, in the nanocrystalline test of synthetic ZnS, mostly adopted toxic substance to make solvent, serious and be unfavorable for realizing industrialization to environmental disruption.
Summary of the invention
Purpose of the present invention, to overcome the bad dispersibility of the prepared ZnS nano material of prior art, mostly adopt toxic substance to do the shortcoming of solvent, a kind of employing solution chemical method is provided, synthetic nanocrystalline without the zink sulphide ZnS of any dephasign and favorable dispersity take the Diethylene Glycol of environmental protection as solvent.
The present invention is achieved by following technical solution:
Prepare pure phase, the nanocrystalline method of monodispersed ZnS with Diethylene Glycol as solvent, have following steps:
(1) configuration precursor liquid
Zinc nitrate hexahydrate is dissolved in the Diethylene Glycol solvent, and configuration zinc source precursor liquid contains 0.1mmolZn (NO in every ml solvent
3)
26H
2O places and is stirred to fully dissolving on the magnetic stirring apparatus; Thioacetamide and polyvinylpyrrolidone abbreviation PVP are dissolved in the Diethylene Glycol solvent, and configuration sulphur source base fluid contains 0.025mmol thioacetamide and 0.00125gPVP in every ml solvent, places electric mantle to be stirred to fully dissolving;
(2) synthetic preparation zinc oxide nanocrystalline
The consoluet sulphur of step (1) source base fluid is poured in the there-necked flask that prolong is housed, pass into nitrogen gas stream, begin to heat with 10 ℃/min from room temperature, when arriving 200 ℃ zinc source precursor liquid is injected sulphur source base fluid at once, wherein zinc source precursor liquid and the mixed Zn:S mol ratio of sulphur source base fluid are 1:1, mixing solutions is stabilized in 180 ℃～200 ℃ backflow 10min, then with being water-cooled to room temperature; Make zinc oxide nanocrystalline product solution.
(3) clean zinc oxide nanocrystalline
Adding isopyknic dehydrated alcohol in the resulting zinc oxide nanocrystalline product of step (2) solution dilutes, be sub-packed in centrifugation under 9000-12000r/min in the centrifuge tube after mixing, so adopt the excessive absolute ethanol washing-eccentric cleaning of 5 times of volumes 3 ~ 5 times, nanocrystalline after the washing is dispersed in airtight preservation in the alcohol the most at last again.
The preferred reflux temperature of described step (2) is 180 ℃.
The invention has the beneficial effects as follows:
This patent adopts the synthetic ZnS nano material of solution chemical method, polar solvent Diethylene Glycol with the environmental protection with higher is made solvent, adding a certain amount of auxiliary has synthesized without the zink sulphide ZnS of any dephasign and favorable dispersity nanocrystalline, whole preparation process green non-pollution, software is simple, and preparation cost is low.The ZnS for preparing favorable dispersity under free of contamination environment is nanocrystalline, is well suited for large-scale industrial production.
Description of drawings
Fig. 1 is the nanocrystalline XRD figure spectrum of gained ZnS of the present invention;
Fig. 2 is the nanocrystalline TEM picture of gained ZnS of the present invention;
Fig. 3 is the nanocrystalline SEM collection of illustrative plates of gained ZnS of the present invention;
Fig. 4 is the nanocrystalline EDS collection of illustrative plates of gained ZnS of the present invention;
Fig. 5 is the nanocrystalline UV-Vis collection of illustrative plates of gained ZnS of the present invention.
Embodiment
The present invention is raw materials used to be commercially available analytical reagent, and specific embodiment is as follows.
(1) configuration precursor liquid
In beaker with 1mmol Zn (NO
3)
26H
2O is dissolved in and does zinc source precursor liquid in the 10ml Diethylene Glycol, places and is stirred to fully dissolving on the magnetic stirring apparatus; In there-necked flask, 1mmol thioacetamide and 0.05gPVP be dissolved in and do sulphur source base fluid in the 40ml Diethylene Glycol, place electric mantle to be stirred to fully dissolving.
(2) synthetic preparation zinc oxide nanocrystalline
The consoluet sulphur of step (1) source base fluid is begun to heat with 10 ℃/min from room temperature, when arriving 200 ℃ zinc source precursor liquid is injected sulphur source base fluid at once, wherein zinc source precursor liquid and the mixed Zn:S mol ratio of sulphur source base fluid are 1:1, mixing solutions is stabilized in 180 ℃ of backflow 10min, then with being water-cooled to room temperature.Whole reaction process all is to carry out passing under the nitrogen protection in there-necked flask.
(3) clean zinc sulfide nano-crystalline
In the resulting zinc sulfide nano-crystalline product of step (2) solution, add 50ml alcohol and mix, be sub-packed in subsequently centrifugation under 9000-12000r/min in the centrifuge tube, so adopt the excessive absolute ethanol washing-eccentric cleaning of 5 times of volumes 4 times, nanocrystalline after the washing is dispersed in airtight preservation in the alcohol the most at last again;
(4) sample test
Extraction step (3) is dispersed in the nanocrystalline suspension in the alcohol, drops on the copper mesh, dries up with blower, as the transmission electron microscope specimen; Nanocrystalline alcohol suspension is diluted to translucent, as the ultraviolet-visible spectrum specimen; Extraction is dispersed in the nanocrystalline suspension in the alcohol, and oven dry and grinding under 60 ℃ in baking oven is as the X-ray diffractometer specimen.
The employing test analytical instrument is as follows:
1, adopts Rigaku D/Max 2500V/PC X-ray diffractometer
The manocrystalline powders aggregate is carried out crystalline phase and particle size analysis.Wherein, operating voltage is 40kV, and working current is 200mA, and scanning angle is 10-90 °, and sweep velocity is 8 °/min.
2, adopt Tecnai G2F20 type field transmission electron microscope that nanocrystalline pattern and crystalline network are carried out low power and high power analysis, observe dispersiveness and growthhabit.
3, adopt Hatchi S-4800 field emission scanning electron microscope that nanocrystal aggregates is carried out the analysis of sample topography, sample is the metal spraying sample.
4, the Genesis XM2 energy spectrometer that adopts Hatchi S-4800 field emission scanning electron microscope to be equipped with carries out the chemical element composition analysis of sample to nanocrystal aggregates, and sample is the metal spraying sample, judges by element ratio whether sample is single-phase.
5, it is the photoabsorption coefficient of 200-900nm that ultraviolet-visible absorption spectroscopy analysis (UV-Vis) adopts the Tu-1901 ultraviolet-visible spectrophotometer to measure wavelength region, and is used for calculating nanocrystalline energy gap.
Fig. 1 is the nanocrystalline XRD figure of gained ZnS of the present invention spectrum, illustrates that what obtain is that single-phase zincblende lattce structure ZnS is nanocrystalline.
Fig. 2 is the nanocrystalline TEM picture of gained ZnS of the present invention, illustrates that what obtain is that monodispersed ZnS is nanocrystalline.
Fig. 3 is the nanocrystalline SEM collection of illustrative plates of gained ZnS of the present invention, illustrates that the nanocrystalline size distribution of ZnS is even.
Fig. 4 is the nanocrystalline EDS collection of illustrative plates of gained ZnS of the present invention, illustrates that what obtain is nanocrystalline near stoichiometric ZnS.
Fig. 5 is the nanocrystalline UV-Vis collection of illustrative plates of gained ZnS of the present invention, illustrates that the nanocrystalline energy gap of the ZnS that obtains is 3.75eV.
Claims (2)
1. one kind prepares pure phase, the nanocrystalline method of monodispersed ZnS with Diethylene Glycol as solvent, has following steps:
(1) configuration precursor liquid
Zinc nitrate hexahydrate is dissolved in the Diethylene Glycol solvent, and configuration zinc source precursor liquid contains 0.1mmolZn (NO in every ml solvent
3)
26H
2O places and is stirred to fully dissolving on the magnetic stirring apparatus; Thioacetamide and polyvinylpyrrolidone abbreviation PVP are dissolved in the Diethylene Glycol solvent, and configuration sulphur source base fluid contains 0.025mmol thioacetamide and 0.00125gPVP in every ml solvent, places electric mantle to be stirred to fully dissolving;
(2) synthetic preparation zinc oxide nanocrystalline
The consoluet sulphur of step (1) source base fluid is poured in the there-necked flask that prolong is housed, pass into nitrogen gas stream, begin to heat with 10 ℃/min from room temperature, when arriving 200 ℃ zinc source precursor liquid is injected sulphur source base fluid at once, wherein zinc source precursor liquid and the mixed Zn:S mol ratio of sulphur source base fluid are 1:1, mixing solutions is stabilized in 180 ℃～200 ℃ backflow 10min, then with being water-cooled to room temperature; Make zinc oxide nanocrystalline product solution.
(3) clean zinc oxide nanocrystalline
Adding isopyknic dehydrated alcohol in the resulting zinc oxide nanocrystalline product of step (2) solution dilutes, be sub-packed in centrifugation under 9000-12000r/min in the centrifuge tube after mixing, so adopt the excessive absolute ethanol washing-eccentric cleaning of 5 times of volumes 3 ~ 5 times, nanocrystalline after the washing is dispersed in airtight preservation in the alcohol the most at last again.
According to claim 1 prepare pure phase, the nanocrystalline method of monodispersed ZnS with Diethylene Glycol as solvent, it is characterized in that the preferred reflux temperature of described step (2) is 180 ℃.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103613117A (en) * | 2013-12-02 | 2014-03-05 | 镇江市高等专科学校 | Method for regulating and controlling zinc sulfide nanoparticle morphology by regulating proportion of mixed solvent |
| CN104609461A (en) * | 2015-01-27 | 2015-05-13 | 张家港汇普光学材料有限公司 | Washing device for zinc sulfide for optical infrared imaging |
| CN105113006A (en) * | 2015-09-21 | 2015-12-02 | 陕西科技大学 | Mono-dispersed spherical zinc sulfide photonic crystal with rough surface and preparation method thereof |
| CN114835154A (en) * | 2022-03-31 | 2022-08-02 | 宁波大学 | Preparation method of monodisperse ZnS colloidal microspheres with adjustable particle size |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101817549A (en) * | 2010-04-02 | 2010-09-01 | 吉林大学 | Cubic crystal zinc sulfide nano-particles and nanocomposite optical thin film prepared thereby |
| CN102515255A (en) * | 2012-01-09 | 2012-06-27 | 西南大学 | Method for preparing zinc sulfide nanospheres |
-
2012
- 2012-11-02 CN CN2012104332295A patent/CN102923759A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101817549A (en) * | 2010-04-02 | 2010-09-01 | 吉林大学 | Cubic crystal zinc sulfide nano-particles and nanocomposite optical thin film prepared thereby |
| CN102515255A (en) * | 2012-01-09 | 2012-06-27 | 西南大学 | Method for preparing zinc sulfide nanospheres |
Non-Patent Citations (1)
| Title |
|---|
| K. R. MURALI: "Characteristics of ZnS films pulse plated using non-aqueous electrolytes", 《J MATER SCI: MATER ELECTRON》, vol. 21, 5 February 2010 (2010-02-05), pages 1293 - 1298, XP019858440, DOI: doi:10.1007/s10854-010-0065-3 * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103613117A (en) * | 2013-12-02 | 2014-03-05 | 镇江市高等专科学校 | Method for regulating and controlling zinc sulfide nanoparticle morphology by regulating proportion of mixed solvent |
| CN103613117B (en) * | 2013-12-02 | 2016-01-06 | 镇江市高等专科学校 | A kind of method adjusting the ratio regulation and control zinc sulfide nano pattern of mixed solvent |
| CN104609461A (en) * | 2015-01-27 | 2015-05-13 | 张家港汇普光学材料有限公司 | Washing device for zinc sulfide for optical infrared imaging |
| CN105113006A (en) * | 2015-09-21 | 2015-12-02 | 陕西科技大学 | Mono-dispersed spherical zinc sulfide photonic crystal with rough surface and preparation method thereof |
| CN114835154A (en) * | 2022-03-31 | 2022-08-02 | 宁波大学 | Preparation method of monodisperse ZnS colloidal microspheres with adjustable particle size |
| CN114835154B (en) * | 2022-03-31 | 2024-01-26 | 宁波大学 | Preparation method of monodisperse ZnS colloidal microspheres with adjustable particle size |
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Application publication date: 20130213 |