CN101519223A - One-step template-free method for preparing a great amount of monodisperse ZnS hollow nanospheres - Google Patents
One-step template-free method for preparing a great amount of monodisperse ZnS hollow nanospheres Download PDFInfo
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Abstract
The invention relates to a one-step template-free method for preparing a great amount of monodisperse ZnS hollow nanospheres. The method comprises the following steps: the zinc acetate is dissolved in distilled water; thiourea is added to the solution and stirred in the solution at the room temperature until the solution is clear; the obtained solution is transferred to a stainless steel reaction vessel with a polytetrafluoroethylene lining for sealing, then the reaction vessel is heated to the reaction temperature and kept at the reaction temperature for 1 to 48 hours, and the thiourea is decomposed and reacts with the zinc acetate to generate deposition; and after the reaction, the reaction vessel is cooled to the room temperature, then the clear solution on the upper layer is removed, and the obtained deposition is washed with the distilled water and dried in a vacuum drying oven at 30-100 DEG C to obtain the monodisperse ZnS hollow nanospheres. By adopting the method, the monodisperse ZnS hollow nanospheres with radius of 200 nm and with casing layers assembled by nano-particles can be prepared at a large scale. The method is simple and environment-friendly, needs lower temperature and no template and additive agent and takes the water as the solvent. The method can prepare other transition metal oxide hollow nanospheres, such as manganese sulfide, cadmium sulfide, and the like.
Description
Technical field
The present invention relates to prepare the method for monodisperse ZnS hollow nanospheres, an one-step template-free method of particularly a large amount of preparation monodisperse ZnS hollow nanospheres.
Technical background
The graded hollow nanostructure has attracted to pay close attention to widely, because they have the peculiar physics-chem characteristic that is different from bulk material fully, and all be widely used in many fields such as nanochemistry reactor, effective catalyst, drug delivery, advanced low-k materials, sound-proof material and optics.The method of traditional preparation process hollow ball generally all needs can remove or consumable template, comprise hard template (as mono-disperse polymer colloid, charcoal ball, silica spheres, reducing metal nano particle) or soft template (as micella, polymer, oil droplet, bubble), form inorganic nanoparticles on its surface by absorption or chemical reaction.But the application of template all can have shortcomings expensive and that preparation process is many usually, thereby influences its large-scale application.The template of contrast multistep, a pot template-free method prepares controlled hollow structure material and has very big advantage.Zinc sulphide has good fluorescent characteristic as a kind of important semiconductor material, also is that a kind of effective catalyst is used to fields such as photochemical catalysis and Pollutant Treatment simultaneously.Up to the present, low-dimensional zinc sulfide nano structure and complicated nanostructure aggregate are produced out.In order to develop the method for efficient cheap mass preparation zinc sulphide hollow ball, this patent has proposed the method that an a kind of simple one-step template-free prepares the monodisperse ZnS hollow ball, promptly utilizes zinc acetate and thiocarbamide to react under hydrothermal condition.
Summary of the invention
The objective of the invention is according to present domestic and international research present situation, consider the deficiency that common preparation zinc sulphide graduation nano-hollow ball method exists, an a kind of one-step template-free method for preparing monodisperse ZnS hollow nanospheres is provided.This method is simple, low temperature, no template and additive, water are solvent, environmental friendliness.Adopting present method can prepare radius in a large number is about 200nm, the monodisperse ZnS hollow nanospheres that shell is assembled by nano particle.
The technical scheme that realizes the object of the invention is:
A kind of a large amount of method for preparing monodisperse ZnS hollow nanospheres is characterized in that this method is an one-step template-free hydrothermal method, and method steps is followed successively by:
1st, zinc acetate is dissolved in the distilled water, being made into concentration is 0.01-0.3mol/L solution;
2nd, in the solution of step 1 gained, press 40mL solution and add thiocarbamide 20-60mmol, and at room temperature be stirred to the solution clarification;
3rd, gained solution is transferred in the teflon-lined stainless steel cauldron sealing after, reactor is heated to 100-200 ℃, kept 1 to 48 hour, thiocarbamide is decomposed produces and precipitate with the zinc acetate reaction;
4th, reacted after, behind the reactor cool to room temperature, discard supernatant liquid, with the precipitation of gained with distilled water wash more than 3 times, then in vacuum drying oven in 30-100 ℃ dry 4-24 hour down, promptly get the monodisperse ZnS hollow nanospheres product.
The described method (experiment optimum condition) for preparing monodisperse ZnS hollow nanospheres is: zinc acetate is dissolved in the distilled water, being made into concentration is 0.01-0.3mol/L solution, in this zinc acetate solution, press 80mL then and add the 30-50mmol thiocarbamide, and at room temperature be stirred to solution clarification, after gained solution transferred in the teflon-lined stainless steel cauldron sealing, reactor is heated to 120-180 ℃, thiocarbamide decomposes and zinc acetate reaction 5-24 hour, precipitation usefulness distilled water wash i more than 3 times, then in vacuum drying oven in 60 ± 2 ℃ of dryings 6 hours, promptly get the monodisperse ZnS hollow nanospheres product.
One one-step template-free method of the said preparation monodisperse ZnS hollow nanospheres of the present invention except that can preparing the zinc sulphide, can also prepare other transition metal oxide nano hollow balls as manganese sulfide, Cadmium Sulfide etc.
The photocatalytic activity of prepared monodisperse ZnS hollow nanospheres is that the rhodamine B by the photocatalytic degradation liquid phase characterizes.Experimentation is as follows: the test of the photocatalytic degradation rhodamine B of ZnS sample is carried out in rhodamine B solution, and the initial concentration of rhodamine B is 1 * 10
-5M.The preparation process of photocatalyst sample is that ZnS suspension evenly is coated onto on the culture dish that diameter is 7cm, with culture dish 100 ℃ down dry, it is stand-by to be cooled to room temperature then.The quality of each test sample is 50mg.During experiment 20 milliliters of rhodamine B solution are added in the culture dish.Before with the xenon lamp irradiation, allow rhodamine B solution and catalyzer reach absorption-desorption balance.The light that shines sample surfaces is 30mW/cm
2The variation of rhodamine B strength of solution detects with ultraviolet-visible spectrophotometer (UV-2550, Shimadzu, Japan).At regular intervals, reaction soln is filtered and collects the variation that detects the rhodamine B strength of solution.
The characterizing method of the microstructure of monodisperse ZnS hollow nanospheres is: at Cu K α is that X-gamma ray source, scanning speed are 0.05 ° of s
-1X-ray diffractometer (HZG41/B-PC type) on X-ray diffraction (XRD) spectrogram of obtaining determine crystalline phase and grain-size.(FESEM, Hitachi Japan) obtain scanning electron microscope image (SEM), and acceleration voltage is 5kV by the S4800 field emission scanning electron microscope.(JEOL-2010F 200kV) comes the size and dimension of observation sample for utilization transmission electron microscope (TEM) and high-resolution-ration transmission electric-lens (HRTEM).To observe the required sample of TEM be at first under ultrasound condition the ZnS powder to be distributed in the dehydrated alcohol, dispersant liquid drop is added to prepare on charcoal-copper complex network then.The specific surface area of powdered sample is that the method by nitrogen absorption is to test on the n2 absorption apparatus device of Micromeritics ASAP 2020 (USA) in model.All samples all outgased 2 hours down at 100 ℃ earlier before test.The Brunauer-Emmett-Teller of sample (BET) surface-area (SBET) is to utilize relative pressure (P/P by the method for multiple spot BET
0) be that the interior adsorpting data of 0.05～0.3 scope calculates.
Desorption isotherm is used for measuring pore size distribution, and by Barret-Joyner-Halender (BJH) method, and the supposition hole is the cylindrical shape hole.With relative pressure (P/P
0) be that 0.994 nitrogen adsorption volume is determined pore volume and mean pore size.
Description of drawings
Fig. 1 is (a) 140 under differing temps, and (b) 170, (c) 180, (d) XRD figure of the ZnS sample of 200 ℃ of reactions preparation in 5 hours
Fig. 2 is at the low power SEM figure of the ZnS sample of 140 ℃ of reactions preparation in 5 hours
Fig. 3 is (a) 140 under differing temps, and (b) 170, (c) the high power SEM figure of the ZnS sample of 180 ℃ of reactions preparation in 5 hours
Fig. 4 is at 170 ℃ of TEM and SAED (inserting figure) that react the ZnS powder of preparation in 5 hours down
Fig. 5 reacts the ZnS of preparation in 5 hours under differing temps
2Nitrogen adsorption-the desorption isotherm of sample
Fig. 6 reacts the pore size distribution curve of the ZnS sample of preparation in 5 hours under differing temps
Reacting the ZnS powder that prepared in 5 hours down with 140 ℃ under Fig. 7 room temperature is catalyzer, and the absorption peak of rhodamine B solution changes under UV-irradiation
Embodiment
The preparation monodisperse ZnS hollow nanospheres
Be used as reactant with zinc acetate and thiocarbamide.The detailed experiments process is as follows:
Zinc acetate 1.6mmol is dissolved in 40 ml distilled waters, in solution, add the 40mmol thiocarbamide then, and at room temperature be stirred to solution clarification, join 4 parts of settled solutions by described method, after respectively gained solution being transferred in the teflon-lined stainless steel cauldron sealing, reactor is heated to is heated to 140,170,180 or 200 ℃ respectively, thiocarbamide is decomposed and zinc acetate reaction 5 hours, precipitation distilled water wash 3 times, then in vacuum drying oven in 60 ± 2 ℃ of dryings 6 hours, promptly get the monodisperse ZnS hollow nanospheres product.
Characterize the phase structure of prepared sample with XRD.The XRD figure of the ZnS sample for preparing under differing temps is shown in Fig. 1.All diffraction peaks can easily be demarcated pure six side's wurtzite phase (JCPDS No.36-1450, the a=3.821 into ZnS as can see from Figure 1
, c=6.257
).(100) and (101) diffraction peak has produced the part crossover with (002) peak because of broadening in the collection of illustrative plates, and this is because smaller grain-size causes.Along with the increase of temperature of reaction, the diffraction peak intensity of six side's phases increases, and the increase of degree of crystallinity and the increase of grain-size are described.Studies show that further temperature of reaction has tangible influence to the degree of crystallinity of ZnS.The grain-size of the ZnS powder that comes out with the peak width at half height data computation of (101) diffraction peak according to the Scherrer equation is increased to 53.5 nanometers from 17.0 nanometers, and the grain-size of prepared ZnS powder increases along with the increase of temperature of reaction.
Fig. 2 and Fig. 3 have provided the SEM image of 5 hours ZnS samples of reaction under the differing temps.Fig. 2 is the low magnification image of 140 ℃ of following gained samples, can see the monodisperse hollow ball about the very big radius of output 200 nanometers.From the high Fig. 3 a of magnification as can be seen the shell of hollow ball be that nano particle by about 15 nanometers of size assembles.Fig. 3 b, 3c are respectively the sample that makes under 170 ℃, 180 ℃, are the hollow ball structures that the particle by the 30-40 nanometer assembles.Yet when being elevated to 200 ℃, temperature can only obtain the aggregate of nano particle; Opposite, when temperature was reduced to below 100 ℃, precipitation did not produce.So best temperature of reaction is 140-180 ℃.
Fig. 4 has provided 170 ℃ of TEM and SAED photos of the ZnS sample of reaction preparation in 5 hours down.Electron density difference on spherical center and the limit has further confirmed hollow structure.The mean sizes of the primary granule of the composition shell of estimating from the TEM photo is approximately 30-40nm, with more identical with the value of Scherrer Equation for Calculating from XRD figure.Further observation can be seen the hole that is produced by nanoparticle aggregate, and this vesicular structure can make that chemical substance is easier to enter in the spheroid.Corresponding electron-diffraction diagram shows that these nanometer balls are polycrystalline.Three diffraction rings at its center correspond respectively to (002), (110) and (112) crystal face of six side's zinc sulphide, and are very identical with the result of XRD.
Fig. 5 has provided the nitrogen adsorption-desorption isotherm of 5 hours samples of reaction under the differing temps.Under 140 ℃, thermoisopleth is IV type (BDDT classification), and its capillary condensation was divided into for three steps, shows to contain mesoporous and macropore in the sample, and have bimodal pore size distribution in mesoporous scope.Wherein mesoporous is cause by assembling between the particle of primary granule, and macropore to be gathering by secondary particle cause.
Fig. 6 has provided the pore size distribution curve of reaction preparation in 5 hours sample correspondence under the differing temps.140 ℃ of samples that prepare down present three peak pore size distributions in mesoporous and macropore scope.Two kinds of mesoporous existence are arranged in the sample, lay respectively at about 3.5nm and 7.0nm, about 60 nanometers, have the distribution of macropore in addition.Along with the increase of temperature of reaction, pore size distribution is distributed by three peaks and changes unimodal distribution gradually into, and the aperture peak value moves right.Pore size distribution change with the aperture peak value move may be because of degree of crystallinity different.In addition, along with the increase of temperature, sample has bigger absorption at relative pressure near 1 place, and the area percentage of whole hysteresis loop under higher relative pressure also significantly increases, and these have shown the growth of macropore and have occupied dominant position at high temperature.
It is catalyzer that Fig. 7 has provided the ZnS powder that prepared in 5 hours with 140 ℃ of following reactions under the room temperature, and the absorption peak of rhodamine B solution changes under UV-irradiation.Rhodamine B has a main absorption peak in 553 nanometers.Under UV-irradiation, absorption peak obviously reduces and follows peak position to move to the shortwave direction.This shows that dyestuff has passed through the ethyl process of taking off progressively, and this can be confirmed by the blue shift that initial redness becomes yellow-green colour and peak value by solution.Color at irradiation solution after 90 minutes disappears, and the decolouring group that shows dyestuff is by completely destroy.In addition, our photocatalysis performance of the sample that makes as reference substance and this experiment with commercial zinc sulphide contrasts.The result shows that the photocatalysis performance of this laboratory sample has significant enhancing, and this is that special appearance by hollow ball causes.Its graduate structure has higher specific surface area and perviousness, and coarse outside surface also can provide more adsorption potential for reaction molecular.In addition, the hollow structure that it is inner and the vesicular structure of shell can increase the scattering of light in duct and spheroid inside, thereby improve the utilising efficiency of light, increase the quantity in the light induced electron-hole that participates in degradation of contaminant.
Embodiment 2:
In order to check the influence of reaction times to sample topography, 40 ℃ of temperature of reaction stuck-at-s, except that the reaction times difference, other reaction conditions as: the amounts of zinc acetate and thiocarbamide etc. are all identical with embodiment 1.The result shows that the sample that prepared at 1 hour is that radius is the solid sphere of 100 nanometers.Along with the reaction times is increased to 5 hours, sample topography becomes the nucleocapsid structure of homogeneous, and radius is increased to 200 nanometers, and it is coarse that the surface becomes.The pattern of the sample of preparation in 10 hours is the hollow ball with bivalve layer.Along with temperature of reaction further be increased to 24 hours, finally obtain having the hollow structure completely of bigger grain-size and thicker shell.Can infer that by above result the growth mechanism of hollow ball is the Ostwald weathering process, promptly little crystal grain dissolves the progressively cavitation processes that generates big crystal grain gradually.So the best reaction times is 5-24 hour.
Embodiment 3:
For the influence of the amount of checking thiocarbamide to sample topography, except that the amount of thiocarbamide is being got between 20-60mmol the different value except that the amount of thiocarbamide, other reaction conditions as: the amounts (40 milliliters) of the amount of zinc acetate (1.6mmol), temperature of reaction (140 ℃), reaction times (5 hours), water etc. are all identical with embodiment 1.The result shows that when the amount of thiocarbamide was reduced to 20mmol, prepared sample was the aggregate of nano particle, and this is because the minimizing of thiocarbamide has reduced itself and the amount of zine ion formation complex compound, thus zine ion homogeneous nucleation in solution; Fall when being elevated to 60mmol when the thiocarbamide amount, prepared sample is the nanometer solid sphere, and this is because the carrying out that too much thiocarbamide has stoped the Ostwald weathering process.The amount of finding best thiocarbamide in the experiment is 30-50mmol.
Embodiment 4:
In order to check the influence of reactant species to sample topography, except that having changed zinc source and sulphur source, other reaction conditions as: the amounts (40 milliliters) of the amount of reactant, temperature of reaction (140 ℃), reaction times (5 hours), distilled water etc. are all identical with embodiment 1.The result shows, is the zinc source when replacing zinc acetate with zinc nitrate, and prepared sample is the aggregate of nano particle; When replacing thiocarbamide with zinc sulphide is the sulphur source, and prepared sample is the mono-dispersed nano particle.
Embodiment 5:
Other transient metal sulfide hollow balls such as Cadmium Sulfide also can pass through method for preparing.Also be by cadmium acetate 1.6mmol is dissolved in 40 ml distilled waters, in solution, add the 40mmol thiocarbamide then, and at room temperature be stirred to solution clarification, after gained solution transferred in the teflon-lined stainless steel cauldron sealing, reactor is heated to 140-200 ℃, and thiocarbamide decomposes and cadmium acetate reaction 5-24 hour, precipitation 3 washings of distilled water, then in vacuum drying oven in 60 ± 2 ℃ of dryings 6 hours, promptly get monodisperse CdS nano-hollow ball product.
Claims (5)
1, a kind of a large amount of method for preparing monodisperse ZnS hollow nanospheres is characterized in that this method is the hydrothermal method of an one-step template-free, and method steps is followed successively by:
1st, zinc acetate is dissolved in the distilled water, being made into concentration is 0.01-0.3mol/L solution; 2nd, in the solution of step 1 gained, press 40mL solution and add thiocarbamide 20-60mmol, and at room temperature be stirred to the solution clarification;
3rd, step 2 gained solution is transferred in the teflon-lined stainless steel cauldron sealing after, reactor is heated to 100-200 ℃, kept 1 to 48 hour, thiocarbamide is decomposed produces and precipitate with the zinc acetate reaction;
4th, reacted after, behind the reactor cool to room temperature, discard supernatant liquid, with the precipitation of gained with distilled water wash more than 3 times, then in vacuum drying oven in 30-100 ℃ dry 4-24 hour down, promptly get the monodisperse ZnS hollow nanospheres product.
2, the method for preparing monodisperse ZnS hollow nanospheres as claimed in claim 1, it is characterized in that: zinc acetate is dissolved in the distilled water, being made into concentration is 0.01-0.3mol/L solution, press then and add the 30-50mmol thiocarbamide in the 80mL solution, and at room temperature be stirred to solution clarification, gained solution is transferred in the teflon-lined stainless steel cauldron sealed.
3, the method for preparing monodisperse ZnS hollow nanospheres as claimed in claim 1 or 2 is characterized in that described reactor is heated to 120-180 ℃.
4,, it is characterized in that the described reaction times is 5-24 hour as claim 1 or the described method for preparing monodisperse ZnS hollow nanospheres.
5, the method for preparing monodisperse ZnS hollow nanospheres as claimed in claim 1 or 2 is characterized in that described exsiccant temperature is 60 ± 2 ℃, and be 6 hours time of drying.
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| CN101844795A (en) * | 2010-03-19 | 2010-09-29 | 中南民族大学 | Preparation method of spiauterite-type zinc sulfide nano-sphere with high photocatalytic activity |
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| CN102107904A (en) * | 2011-03-11 | 2011-06-29 | 同济大学 | Method for preparing cadmium sulfide or zinc sulfide hollow nano diamonds by using non-template method |
| CN102107904B (en) * | 2011-03-11 | 2012-06-06 | 同济大学 | Method for preparing cadmium sulfide or zinc sulfide hollow nano diamonds by using non-template method |
| CN103803636B (en) * | 2012-11-14 | 2015-04-22 | 上海纳米技术及应用国家工程研究中心有限公司 | Preparation method of zinc sulfide nuclear hollow microspheres |
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| CN107001153A (en) * | 2014-07-10 | 2017-08-01 | 国立科学研究中心 | The method for manufacturing the ceramic component based on sulfide, particularly for IR optical applications |
| 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 |
| CN106319632A (en) * | 2016-08-02 | 2017-01-11 | 淮阴工学院 | Zinc sulfide twin nanosphere and preparation method thereof |
| CN106927498A (en) * | 2017-03-14 | 2017-07-07 | 中南大学 | A kind of zinc sulfide nano-belt, preparation and its application in lithium sulfur battery anode material is prepared |
| CN106927498B (en) * | 2017-03-14 | 2019-08-16 | 中南大学 | A kind of zinc sulfide nano-belt, preparation and its preparing the application in lithium sulfur battery anode material |
| CN114455629A (en) * | 2022-01-27 | 2022-05-10 | 扬州大学 | Preparation method of ternary composite material for gas sensing and product thereof |
| CN114455629B (en) * | 2022-01-27 | 2023-05-26 | 扬州大学 | Preparation method of ternary composite material for gas sensing and product thereof |
| CN114988458A (en) * | 2022-06-15 | 2022-09-02 | 江西八六三实业有限公司 | Method for preparing ZnS crystal based on control of morphology of copper-based catalyst |
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