CN102941045A - Method for preparing multiple nano-composite balls with uniform size and CdS-C core-shell structures shaped like trivalvular flowers - Google Patents
Method for preparing multiple nano-composite balls with uniform size and CdS-C core-shell structures shaped like trivalvular flowers Download PDFInfo
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- CN102941045A CN102941045A CN2012104668944A CN201210466894A CN102941045A CN 102941045 A CN102941045 A CN 102941045A CN 2012104668944 A CN2012104668944 A CN 2012104668944A CN 201210466894 A CN201210466894 A CN 201210466894A CN 102941045 A CN102941045 A CN 102941045A
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Abstract
The invention provides a method for preparing multiple nano-composite balls with uniform size and CdS-C core-shell structures shaped like trivalvular flowers. The method for preparing the multiple nano-composite balls with uniform size and CdS-C core-shell structures shaped like the trivalvular flowers is as follows: glycol is utilized as a solvent, transition metal inorganic salt cadmium chloride (CdCl2.2.5H2O) as a reaction precursor, a surfactant polyvinyl pyrrolidone (PVP) and a certain amount of thiocarbamide (TU) and glucose are added, a solvothermal method is adopted to control the vulcanization of the reaction predecessor and the appearance of a product, so that the high-quality and high-yield nano-composite balls with uniform size and CdS-C core-shell structures shaped like the trivalvular flowers are obtained. The nano-composite balls with uniform size and CdS-C core-shell structures shaped like the trivalvular flowers, prepared by the method provided by the invention, have the diameter range of 300-400nm and have the advantages of low product cost, easiness in control, high uniformity, high yield, good repeatability, suitability for large scale production, and the like.
Description
Technical field
The invention belongs to nano material and the preparing technical field thereof of CdS, particularly the method for the uniform three hemp nettle shape CdS-C nuclear shell structured nano-composite balls of a kind of a large amount of preparation.
Background technology
Cadmium sulfide (CdS) is a kind of typical II-IV family semiconducting compound, and energy gap is 2.42eV under the room temperature, is a kind of direct band-gap semicondictor, has excellent light transfer characteristic and luminescent properties.The variation with pattern of reducing along with size, obvious variation can occur in the energy gap of cadmium sulfide nanostructure, show and be different from bulk and more excellent photoelectric properties, thereby aspect the new materials such as light emitting diode, solar cell, nonlinear optical material widely purposes is being arranged, especially aspect photocatalysis, attracted various countries scientists' common concern.At " the physical chemistry magazine C " of U.S. magazine (2008,7363 pages of 112 volumes) report was arranged.
At present, the existing bibliographical information method for preparing the CdS nano semiconductor material has: alternately chemical method, microemulsion method, precursor thermal decomposition method, physical vaporous deposition, template etc. are multiple.But the homogeneity of the CdS of these methods preparation is not fine, and preparation method very complicated comparatively.At present, preparing the commonplace method of CdS is hydro-thermal method, " material wall bulletin " magazine of Holland (2010,439 pages of 64 volumes) and " macromolecule circular " magazine (2012 of Germany, 2061 pages of 68 volumes) report was arranged, patent 200810062243.2,200710043458 etc. also discloses the synthetic method of CdS, hydro-thermal method owing to reaction condition gentleness, product advantages of good crystallization, pollute less, be easy to the favor that the advantage such as commercialization enjoys the researcher.In addition, patent 200710100550.0 and 200610049153.0 etc. also discloses the synthetic method of CdS nano semiconductor material, these methods mostly adopt toxic reagent (such as ethylenediamine) as solvent, and also there are the shortcomings such as cost of manufacture is relatively high in the method simultaneously.Rarely have report and adopt chemical method to prepare CdS-C nucleocapsid structure compound, at " material science " magazine (2011,6975 pages of 46 volumes) of Germany report arranged, but the CdS-C nucleocapsid structure compound uniformity of these methods preparations bad, yield poorly.In addition, adopt ethylene glycol as solvent, one-step method prepares the CdS-C composite also report.
Summary of the invention
The objective of the invention is to adopt toxic reagent (such as ethylenediamine) as solvent for existing preparation CdS nano semiconductor material method is existing when CdS nano semiconductor material synthetic, preparation cost is high, building-up process is complicated, wayward, the uniformity of product is low, output is few, the weak point of poor repeatability, a kind of solvent avirulence that adopts when CdS nano semiconductor material synthetic is provided, preparation cost is low, building-up process is very simple, easy to control, the product uniformity is high, output is large, the method of the uniform three hemp nettle shape CdS-C nuclear shell structured nano-composite balls of a kind of a large amount of preparations of good reproducibility.
Technical scheme of the present invention realizes in the following way: the method for the uniform three hemp nettle shape CdS-C nuclear shell structured nano-composite balls of a kind of a large amount of preparations, and adopt ethylene glycol as solvent, adopt the inorganic salts caddy (CdCl of transition metal
22.5H
2O) be pre-reaction material, add surfactant polyvinylpyrrolidone (PVP) and a certain amount of thiocarbamide (TU) and glucose, take sulfuration and the product pattern of the method control pre-reaction material of solvent heat, thereby obtain three hemp nettle shape CdS-C nuclear shell structured nano-composite balls of high-quality, high yield.
In the method for the uniform three hemp nettle shape CdS-C nuclear shell structured nano-composite balls of described a kind of a large amount of preparations, the method for preparing three hemp nettle shape CdS-C nuclear shell structured nano-composite balls may further comprise the steps:
⑴ get raw material caddy (CdCl
22.5H
2O), thiocarbamide, PVP and glucose is dissolved in a certain amount of ethylene glycol, forms homogeneous solution through ultrasonic dispersion, then stirs 15～20 minutes, obtains mixed liquor;
⑵ put into reactor with the mixed liquor that step ⑴ obtains, through 160～180 ℃, 6～12 hours, after naturally cooling to room temperature, open reactor, centrifugal with deionized water and absolute ethanol washing, dry sediment namely obtains three hemp nettle shape CdS-C nuclear shell structured nano-composite balls of different C layer thicknesses.
Adopt three hemp nettle shape CdS-C nuclear shell structured nano-composite balls of the present invention's preparation, its diameter range is at 300～400nm, the advantages such as three hemp nettle shape CdS-C nuclear shell structured nano-composite balls of the present invention's preparation have that product cost is low, easy to control, uniformity is high, output is large, good reproducibility and suitable large-scale production.
Description of drawings
Fig. 1 is the x-ray diffraction pattern of three hemp nettle shape CdS-C nuclear shell structured nano-composite balls of preparation in the example 1,2,3,4 surveyed of the Dutch PW3040/60 of PHILIPS Co. type x-ray diffractometer, CdS-C-glucose (0.5g), CdS-C-glucose (0.25g), CdS-C-glucose (0.75g), CdS-C-glucose (1g) is the x-ray diffraction pattern of representative instance 1,2,3,4 prepared three hemp nettle shape CdS-C nuclear shell structured nano-composite balls respectively, wherein: abscissa X is angle of diffraction (2 θ), and ordinate Y is relative diffracted intensity.
Fig. 2 is a large amount of three hemp nettle shape CdS-C nuclear shell structured nano-composite balls pattern figure of preparation in the S-4800 of HIT type field emission scanning electron microscope (FE-SEM) the observation example 1; Illustration is the pattern enlarged drawing.Product is three hemp nettle shape CdS-C nuclear shell structured nano-composite balls.
Fig. 3 is the corresponding C layer thickness of three hemp nettle shape CdS-C nuclear shell structured nano-composite balls of preparation among the embodiment 1 that observes of JEM-2100F high resolution transmission electron microscopy (HRTEM).
Fig. 4 is the corresponding C layer thickness of three hemp nettle shape CdS-C nuclear shell structured nano-composite balls of preparation among the embodiment 2 that observes of JEM-2100F high resolution transmission electron microscopy (HRTEM).
Fig. 5 is the corresponding C layer thickness of three hemp nettle shape CdS-C nuclear shell structured nano-composite balls of preparation among the embodiment 3 that observes of JEM-2100F high resolution transmission electron microscopy (HRTEM).
Fig. 6 is the corresponding C layer thickness of three hemp nettle shape CdS-C nuclear shell structured nano-composite balls of preparation among the embodiment 4 that observes of JEM-2100F high resolution transmission electron microscopy (HRTEM).
The specific embodiment
Below by embodiment the method for the uniform three hemp nettle shape CdS-C nuclear shell structured nano-composite balls of a kind of a large amount of preparations of the present invention is made further and to be specified, but the present invention is not limited in these examples.
Embodiment 1
Take by weighing 0.7993g(3.5mmol) CdCl
22.5H
2O, 0.2663g(3.5mmol) thiocarbamide, 0.5g glucose and 0.389g(3.5mmol) PVP is dissolved in the 35mL ethylene glycol, forms homogeneous solution through ultrasonic dispersion, then stirs 15～20 minutes, stop to stir.Above-mentioned gained mixed solution is put into the 50mL reactor, through 160～180 ℃ the reaction 6～12 hours after, get suspension, again through centrifuge washing, 60 ℃ of oven dry, sample label CdS-C-glucose (0.5g) is made X-ray diffraction, field emission scanning electron microscope and tem study to products obtained therefrom.
Do the X-ray diffraction analysis for the three hemp nettle shape CdS-C nuclear shell structured nano-composite balls that prepare in this example, the result is shown in CdS-C-glucose (0.5g) among Fig. 1, and its abscissa X is angle of diffraction (2 θ), and ordinate Y is relative diffracted intensity; Among Fig. 1 all diffraction maximums of CdS-C-glucose (0.5g) sample all with lattice paprmeter
With
Six side's phase CdS identical, with the JCPDS in the international standard powder X-ray RD diffraction card, 41-1049 is consistent.
Do the field emission scanning electron microscope analysis for the three hemp nettle shape CdS-C nuclear shell structured nano-composite balls that prepare in this example, the electromicroscopic photograph that obtains as shown in Figure 2, the output that can find out three hemp nettle shape CdS-C nuclear shell structured nano-composite balls is very large, and size is even, and diameter is greatly about about 350nm.
Do the high resolution transmission electron microscopy analysis for the three hemp nettle shape CdS-C nuclear shell structured nano-composite balls that prepare in this example.As can be seen from Figure 3, three hemp nettle shape CdS-C nuclear shell structured nano-composite balls crystallization situations of this example preparation are fine, demonstrate good lattice fringe picture.And can see clearly that the charcoal layer is coated on outside the CdS, the C layer thickness is about 3.9nm.
Example 2
Take by weighing 0.7993g(3.5mmol) CdCl
22.5H
2O, 0.2663g(3.5mmol) thiocarbamide, 0.25g glucose and 0.389g(3.5mmol) PVP is dissolved in the 35mL ethylene glycol, forms homogeneous solution through ultrasonic dispersion, then stirs 15～20 minutes, stop to stir.Above-mentioned gained mixed solution is put into the 50mL reactor, after 6～12 hours, get suspension through 160～180 ℃ of reactions, again through centrifuge washing, 60 ℃ of oven dry, sample label CdS-C-glucose (0.5g).Do X-ray diffraction, field emission scanning electron microscope and high-resolution-ration transmission electric-lens analysis for the product for preparing in this example.
Do the X-ray diffraction analysis for the three hemp nettle shape CdS-C nuclear shell structured nano-composite balls that prepare in this example, the result is shown in CdS-C-glucose (0.25g) among Fig. 1, and its abscissa X is angle of diffraction (2 θ), and ordinate Y is relative diffracted intensity; All diffraction maximums of CdS-C-glucose (0.25g) sample are all consistent with the peak of sample CdS-C-glucose (0.5g) of preparation in the example 1 among Fig. 1.
Similar to example 1 through the scanning electron microscopic observation result for the sample for preparing in this example, the high-resolution-ration transmission electric-lens photo that obtains as shown in Figure 4, the three hemp nettle shape CdS-C nuclear shell structured nano-composite balls (sample label CdS-C-glucose (0.25g)) that prepare in this example as can be observed from Figure have the interface of obvious C and CdS, and the C layer thickness is about 2.4nm.
Example 3
Take by weighing 0.7993g(3.5mmol) CdCl
22.5H
2O, 0.2663g(3.5mmol) thiocarbamide, 0.75g glucose and 0.389g(3.5mmol) PVP is dissolved in the 35mL ethylene glycol, forms homogeneous solution through ultrasonic dispersion, then stirs 15～20 minutes, stop to stir.Above-mentioned gained mixed solution is put into the 50mL reactor, through 160～180 ℃ the reaction 6～12 hours after, get suspension, again through centrifuge washing, 60 ℃ of oven dry, sample label CdS-C-glucose (0.75g) is done X-ray diffraction, field emission scanning electron microscope and high-resolution-ration transmission electric-lens analysis for the product for preparing in this example.
Do the X-ray diffraction analysis for the three hemp nettle shape CdS-C nuclear shell structured nano-composite balls that prepare in this example, the result is shown in CdS-C-glucose (0.75g) among Fig. 1, and its abscissa X is angle of diffraction (2 θ), and ordinate Y is relative diffracted intensity; All diffraction maximums of CdS-C-glucose (0.75g) sample are all consistent with the peak of sample CdS-C-glucose (0.5g) of preparation in the example 1 among Fig. 1.
Similar to example 1 through the scanning electron microscopic observation result for the sample for preparing in this example, the high-resolution-ration transmission electric-lens photo that obtains as shown in Figure 5, the three hemp nettle shape CdS-C nuclear shell structured nano-composite balls (sample label CdS-C-glucose (0.75g)) that prepare in this example as can be observed from Figure have the interface of obvious C and CdS, and the C layer thickness is about 4.7nm.
Example 4
Take by weighing 0.7993g(3.5mmol) CdCl
22.5H
2O, 0.2663g(3.5mmol) thiocarbamide, 1g glucose and 0.389g(3.5mmol) PVP is dissolved in the 35mL ethylene glycol, forms homogeneous solution through ultrasonic dispersion, then stirs 15～20 minutes, stop to stir.Above-mentioned gained mixed solution is put into the 50mL reactor, through 160～180 ℃ the reaction 6～12 hours after, get suspension, again through centrifuge washing, 60 ℃ of oven dry, sample label CdS-C-glucose (1g) is done X-ray diffraction, field emission scanning electron microscope and high-resolution-ration transmission electric-lens analysis for the product for preparing in this example.
Do the X-ray diffraction analysis for the three hemp nettle shape CdS-C nuclear shell structured nano-composite balls that prepare in this example, the result is shown in CdS-C-glucose (1g) among Fig. 1, and its abscissa X is angle of diffraction (2 θ), and ordinate Y is relative diffracted intensity; All diffraction maximums of CdS-C-glucose (1g) sample are all consistent with the peak of sample CdS-C-glucose (0.5g) of preparation in the example 1 among Fig. 1.
Similar to example 1 through the scanning electron microscopic observation result for the sample for preparing in this example, the high-resolution-ration transmission electric-lens photo that obtains as shown in Figure 6, the three hemp nettle shape CdS-C nuclear shell structured nano-composite balls (sample label CdS-C-glucose (1g)) that prepare in this example as can be observed from Figure have the interface of obvious C and CdS, and the C layer thickness is about 6nm.
XRD, FE-SEM, TEM, measurement result and the literature search of HRTEM show: adopt the preparation-obtained three hemp nettle shape CdS-C nuclear shell structured nano-composite balls of the inventive method, it is the low cost that successfully synthesizes with present better simply method, high yield, high-purity, the size homogeneous, the three hemp nettle shape CdS-C nuclear shell structured nano-composite balls that the C layer thickness is controlled, it has been filled up a step solvent-thermal method and has prepared the blank of CdS-C nuclear shell structured nano-composite in synthetic field, for the further exploitation of synthetic CdS-C nuclear shell structured nano-material, application can be played certain impetus.
Claims (2)
1. the method for the uniform three hemp nettle shape CdS-C nuclear shell structured nano-composite balls of a large amount of preparations, it is characterized in that preparing in the method for three hemp nettle shape CdS-C nuclear shell structured nano-composite balls at this, adopt ethylene glycol as solvent, adopt the inorganic salts caddy (CdCl of transition metal
22.5H
2O) be pre-reaction material, add surfactant polyvinylpyrrolidone (PVP) and a certain amount of thiocarbamide (TU) and glucose, take sulfuration and the product pattern of the method control pre-reaction material of solvent heat, thereby obtain three hemp nettle shape CdS-C nuclear shell structured nano-composite balls.
2. the method for the uniform three hemp nettle shape CdS-C nuclear shell structured nano-composite balls of a kind of a large amount of preparations according to claim 1 is characterized in that the method for preparing three hemp nettle shape CdS-C nuclear shell structured nano-composite balls may further comprise the steps:
⑴ get raw material caddy (CdCl
22.5H
2O), thiocarbamide, PVP and glucose is dissolved in a certain amount of ethylene glycol, forms homogeneous solution through ultrasonic dispersion, then stirs 15～20 minutes, obtains mixed liquor;
⑵ put into reactor with the mixed liquor that step ⑴ obtains, through 160～180 ℃, 6～12 hours, after naturally cooling to room temperature, open reactor, centrifugal with deionized water and absolute ethanol washing, dry sediment namely obtains three hemp nettle shape CdS-C nuclear shell structured nano-composite balls of different C layer thicknesses.
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| CN108212195A (en) * | 2018-02-09 | 2018-06-29 | 信阳师范学院 | Petal-shaped cadmium sulfide carbonitride heterojunction nanometer material and preparation method thereof |
| CN114308075A (en) * | 2021-11-30 | 2022-04-12 | 淮阴工学院 | Efficient and stable visible light photocatalyst and preparation method thereof |
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