CN102941045B - 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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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 race's semiconducting compound, and under room temperature, energy gap is 2.42eV, is a kind of direct band-gap semicondictor, has excellent light transfer characteristic and luminescent properties.Along with the reduction of size and the change of pattern, obvious change can be there is in the energy gap of cadmium sulfide nanostructure, show and be different from bulk and more excellent photoelectric properties, thus in the new materials such as light emitting diode, solar cell, nonlinear optical material, purposes is widely had, especially, in photocatalysis, the common concern of various countries scientist has been attracted.Report was had at " physical chemistry magazine C " magazine (2008,112 volumes 7363 pages) of the U.S..
At present, the method that existing bibliographical information prepares CdS nano semiconductor material has: alternating chemistries method, microemulsion method, precursor thermal decomposition method, physical vaporous deposition, template etc. are multiple.But the homogeneity of CdS prepared by these methods is not fine, and preparation method comparatively very complicated.At present, preparing the commonplace method of CdS is hydro-thermal method, at " material bulletin " magazine (2010 of Holland, 64 volumes 439 pages) and " macromolecule circular " magazine (2012 of Germany, 68 volumes 2061 pages) there is report, patent 200810062243.2,200710043458 etc. also discloses the synthetic method of CdS, hydro-thermal method due to reaction condition gentleness, product advantages of good crystallization, pollute less, be easy to the advantages such as commercialization and enjoy the favor of 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 (as ethylenediamine) as solvent, and the method also exists the shortcomings such as cost of manufacture is relatively high simultaneously.And adopt chemical method to prepare CdS-C nucleocapsid structure compound to rarely have report, had report at " material science " magazine (2011,46 volumes 6975 pages) of Germany, but CdS-C nucleocapsid structure compound uniformity prepared by these methods bad, yield poorly.In addition, adopt ethylene glycol as solvent, one-step method prepares CdS-C composite does not also have report.
Summary of the invention
The object of the invention is toxic reagent (as ethylenediamine) need be adopted as solvent for during the existing synthesis at CdS nano semiconductor material prepared existing for CdS nano semiconductor material method, 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, the nontoxic solvent adopted during a kind of synthesis at CdS nano semiconductor material is provided, preparation cost is low, building-up process is very simple, easy to control, 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 reproducible a kind of a large amount of preparation.
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 preparation, adopts ethylene glycol as solvent, adopts 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 the method for solvent heat to control sulfuration and the product morphology of pre-reaction material, thus 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 preparation, the method preparing three hemp nettle shape CdS-C nuclear shell structured nano-composite balls comprises the following steps:
(1) get raw material caddy (CdCl
22.5H
2o), thiocarbamide, PVP and glucose is dissolved in a certain amount of ethylene glycol, forms homogeneous solution, then stir 15 ~ 20 minutes, obtain mixed liquor through ultrasonic disperse;
(2) the mixed liquor that (1) step obtains is put into reactor, through 160 ~ 180 DEG C, 6 ~ 12 hours, reactor is opened after naturally cooling to room temperature, with deionized water and absolute ethanol washing centrifugal, dry sediment, namely obtains three hemp nettle shape CdS-C nuclear shell structured nano-composite balls of different C layer thickness.
Adopt three hemp nettle shape CdS-C nuclear shell structured nano-composite balls prepared by the present invention, its diameter range at 300 ~ 400nm, the advantage such as three hemp nettle shape CdS-C nuclear shell structured nano-composite balls prepared by the present invention have that product cost is low, easy to control, uniformity is high, output is large, reproducible and applicable large-scale production.
Accompanying drawing explanation
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 Dutch PHILIPS Co. PW3040/60 type x-ray diffractometer, the x-ray diffraction pattern of CdS-C-glucose (0.5g), CdS-C-glucose (0.25g), CdS-C-glucose (0.75g), CdS-C-glucose (1g) three hemp nettle shape CdS-C nuclear shell structured nano-composite balls respectively prepared by representative instance 1,2,3,4, wherein: abscissa X is angle of diffraction (2 θ), and ordinate Y is relative diffracted intensity.
A large amount of three hemp nettle shape CdS-C nuclear shell structured nano-composite balls shape appearance figures of preparation in example 1 observed by Tu2Shi HIT S-4800 type field emission scanning electron microscope (FE-SEM); Illustration is pattern enlarged drawing.Product is three hemp nettle shape CdS-C nuclear shell structured nano-composite balls.
Fig. 3 is the C layer thickness corresponding to three hemp nettle shape CdS-C nuclear shell structured nano-composite balls of preparation in the embodiment 1 that observes of JEM-2100F high resolution transmission electron microscopy (HRTEM).
Fig. 4 is the C layer thickness corresponding to three hemp nettle shape CdS-C nuclear shell structured nano-composite balls of preparation in the embodiment 2 that observes of JEM-2100F high resolution transmission electron microscopy (HRTEM).
Fig. 5 is the C layer thickness corresponding to three hemp nettle shape CdS-C nuclear shell structured nano-composite balls of preparation in the embodiment 3 that observes of JEM-2100F high resolution transmission electron microscopy (HRTEM).
Fig. 6 is the C layer thickness corresponding to three hemp nettle shape CdS-C nuclear shell structured nano-composite balls of preparation in the embodiment 4 that observes of JEM-2100F high resolution transmission electron microscopy (HRTEM).
Detailed description of the invention
Make below by the method for embodiment to the uniform three hemp nettle shape CdS-C nuclear shell structured nano-composite balls of a kind of a large amount of preparation of the present invention and further illustrating, but the present invention is not limited in these examples.
Embodiment 1
Take 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 35mL ethylene glycol, forms homogeneous solution, then stir 15 ~ 20 minutes through ultrasonic disperse, stop stirring.Above-mentioned gained mixed solution is put into 50mL reactor, through 160 ~ 180 DEG C of reactions after 6 ~ 12 hours, get suspension, again through centrifuge washing, 60 DEG C of oven dry, sample label CdS-C-glucose (0.5g), makes X-ray diffraction, field emission scanning electron microscope and tem study to products obtained therefrom.
Do X-ray diffraction analysis for the three hemp nettle shape CdS-C nuclear shell structured nano-composite balls prepared in this example, result is as shown in CdS-C-glucose (0.5g) in Fig. 1, and its abscissa X is angle of diffraction (2 θ), and ordinate Y is relative diffracted intensity; In Fig. 1 all diffraction maximums of CdS-C-glucose (0.5g) sample all with lattice paprmeter
with
six side phase CdS identical, with the JCPDS in international standard powder X-ray RD diffraction card, 41-1049 is consistent.
Field emission scanning electron microscope analysis is done for the three hemp nettle shape CdS-C nuclear shell structured nano-composite balls prepared in this example, the electromicroscopic photograph obtained as shown in Figure 2, can find out that the output of three hemp nettle shape CdS-C nuclear shell structured nano-composite balls is very large, size is even, and diameter is greatly about about 350nm.
High resolution transmission electron microscopy analysis is done for the three hemp nettle shape CdS-C nuclear shell structured nano-composite balls prepared in this example.As can be seen from Figure 3, three hemp nettle shape CdS-C nuclear shell structured nano-composite balls crystallization situations prepared by this example are fine, demonstrate good lattice fringe picture.And clearly can see that layer of charcoal is coated on outside CdS, C layer thickness is about 3.9nm.
Example 2
Take 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 35mL ethylene glycol, forms homogeneous solution, then stir 15 ~ 20 minutes through ultrasonic disperse, stop stirring.Above-mentioned gained mixed solution is put into 50mL reactor, after 6 ~ 12 hours, gets suspension through 160 ~ 180 DEG C of reactions, then through centrifuge washing, 60 DEG C of oven dry, sample label CdS-C-glucose (0.5g).X-ray diffraction, field emission scanning electron microscope and high-resolution-ration transmission electric-lens analysis are done for the product prepared in this example.
Do X-ray diffraction analysis for the three hemp nettle shape CdS-C nuclear shell structured nano-composite balls prepared in this example, result is as shown in CdS-C-glucose (0.25g) in Fig. 1, and its abscissa X is angle of diffraction (2 θ), and ordinate Y is relative diffracted intensity; In Fig. 1, all diffraction maximums of CdS-C-glucose (0.25g) sample are all consistent with the peak of the sample CdS-C-glucose (0.5g) prepared in example 1.
Similar to example 1 through scanning electron microscopic observation result for the sample prepared in this example, the high-resolution-ration transmission electric-lens photo obtained 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)) prepared in this example as can be observed from Figure have the interface of obvious C and CdS, and C layer thickness is about 2.4nm.
Example 3
Take 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 35mL ethylene glycol, forms homogeneous solution, then stir 15 ~ 20 minutes through ultrasonic disperse, stop stirring.Above-mentioned gained mixed solution is put into 50mL reactor, through 160 ~ 180 DEG C of reactions after 6 ~ 12 hours, get suspension, again through centrifuge washing, 60 DEG C of oven dry, sample label CdS-C-glucose (0.75g), does X-ray diffraction, field emission scanning electron microscope and high-resolution-ration transmission electric-lens analysis for the product prepared in this example.
Do X-ray diffraction analysis for the three hemp nettle shape CdS-C nuclear shell structured nano-composite balls prepared in this example, result is as shown in CdS-C-glucose (0.75g) in Fig. 1, and its abscissa X is angle of diffraction (2 θ), and ordinate Y is relative diffracted intensity; In Fig. 1, all diffraction maximums of CdS-C-glucose (0.75g) sample are all consistent with the peak of the sample CdS-C-glucose (0.5g) prepared in example 1.
Similar to example 1 through scanning electron microscopic observation result for the sample prepared in this example, the high-resolution-ration transmission electric-lens photo obtained 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)) prepared in this example as can be observed from Figure have the interface of obvious C and CdS, and C layer thickness is about 4.7nm.
Example 4
Take 0.7993g(3.5mmol) CdCl
22.5H
2o, 0.2663g(3.5mmol) thiocarbamide, 1g glucose and 0.389g(3.5mmol) PVP is dissolved in 35mL ethylene glycol, forms homogeneous solution, then stir 15 ~ 20 minutes through ultrasonic disperse, stop stirring.Above-mentioned gained mixed solution is put into 50mL reactor, through 160 ~ 180 DEG C of reactions after 6 ~ 12 hours, get suspension, again through centrifuge washing, 60 DEG C of oven dry, sample label CdS-C-glucose (1g), does X-ray diffraction, field emission scanning electron microscope and high-resolution-ration transmission electric-lens analysis for the product prepared in this example.
Do X-ray diffraction analysis for the three hemp nettle shape CdS-C nuclear shell structured nano-composite balls prepared in this example, result is as shown in CdS-C-glucose (1g) in Fig. 1, and its abscissa X is angle of diffraction (2 θ), and ordinate Y is relative diffracted intensity; In Fig. 1, all diffraction maximums of CdS-C-glucose (1g) sample are all consistent with the peak of the sample CdS-C-glucose (0.5g) prepared in example 1.
Similar to example 1 through scanning electron microscopic observation result for the sample prepared in this example, the high-resolution-ration transmission electric-lens photo obtained as shown in Figure 6, the three hemp nettle shape CdS-C nuclear shell structured nano-composite balls (sample label CdS-C-glucose (1g)) prepared in this example as can be observed from Figure have the interface of obvious C and CdS, and 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 successfully synthesized by current better simply method, high yield, high-purity, size is homogeneous, the three hemp nettle shape CdS-C nuclear shell structured nano-composite balls that 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 synthesis field, for the further exploitation of synthesis CdS-C nuclear shell structured nano-material, application can play certain impetus.
Claims (1)
1. prepare the method for uniform three hemp nettle shape CdS-C nuclear shell structured nano-composite balls in a large number for one kind, prepare 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 thiocarbamide (TU) and glucose, it is characterized in that the method that this prepares three hemp nettle shape CdS-C nuclear shell structured nano-composite balls comprises the following steps:
(1) get raw material caddy (CdCl
22.5H
2o), thiocarbamide (TU), polyvinylpyrrolidone (PVP), glucose and ethylene glycol, wherein, the proportioning of caddy (CdCl22.5H2O), thiocarbamide, polyvinylpyrrolidone (PVP), glucose and ethylene glycol is:
Above-mentioned raw materials is formed homogeneous solution through ultrasonic disperse, then stirs 15 ~ 20 minutes, obtain mixed liquor;
(2) the mixed liquor that (1) step obtains is put into reactor, through 160 ~ 180 DEG C, 6 ~ 12 hours, reactor is opened after naturally cooling to room temperature, get suspension, use again deionized water and absolute ethanol washing centrifugal, 60 DEG C dry sediments, namely obtain three hemp nettle shape CdS-C nuclear shell structured nano-composite balls of different C layer thickness.
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| CN106513017A (en) * | 2016-10-26 | 2017-03-22 | 华南理工大学 | Compound photocatalytic material and preparation method and application thereof |
| CN106732657A (en) * | 2016-11-30 | 2017-05-31 | 浙江师范大学 | A kind of method that easy preparation charcoal bag covers Cu doping CdS flower-like nanometer composite construction photochemical catalysts |
| 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 |
| CN114308075B (en) * | 2021-11-30 | 2023-06-20 | 淮阴工学院 | Efficient and stable visible light photocatalyst and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1792811A (en) * | 2005-11-23 | 2006-06-28 | 南京师范大学 | Process for preparing nano-grade cadmium sufide hollow ball |
| CN101058437A (en) * | 2007-04-10 | 2007-10-24 | 安徽大学 | Liquid state preparation method for nano cadmium sulfide hollow sphere |
| CN101113016A (en) * | 2007-07-05 | 2008-01-30 | 复旦大学 | Preparation method of starfish-shaped cadmium sulfide nanostructure |
| CN101319404A (en) * | 2008-06-10 | 2008-12-10 | 浙江大学 | Method for preparation of hollow spherical cadmium sulfide nanocrystalline |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4096330B2 (en) * | 2002-02-27 | 2008-06-04 | 独立行政法人科学技術振興機構 | Core / shell structure having controlled voids inside, structure using it as a constituent element, and method for preparing them |
| KR100759716B1 (en) * | 2006-09-26 | 2007-10-04 | 고려대학교 산학협력단 | Bifunctional magnetic core- semiconductor shell nanoparticles and manufacturing method thereof |
-
2012
- 2012-11-16 CN CN201210466894.4A patent/CN102941045B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1792811A (en) * | 2005-11-23 | 2006-06-28 | 南京师范大学 | Process for preparing nano-grade cadmium sufide hollow ball |
| CN101058437A (en) * | 2007-04-10 | 2007-10-24 | 安徽大学 | Liquid state preparation method for nano cadmium sulfide hollow sphere |
| CN101113016A (en) * | 2007-07-05 | 2008-01-30 | 复旦大学 | Preparation method of starfish-shaped cadmium sulfide nanostructure |
| CN101319404A (en) * | 2008-06-10 | 2008-12-10 | 浙江大学 | Method for preparation of hollow spherical cadmium sulfide nanocrystalline |
Non-Patent Citations (2)
| Title |
|---|
| An improvedpyrolysisroutetosynthesizecarbon-coatedCdSquantumdots;Kejie Zhang,XiaohengLiu;《Journal of Solid State Chemistry》;20110816(第184期);2701-2706 * |
| One-step construction of ZnS/C and CdS/C one-dimensional core–shell;Xiaoping Shen 等;《Journal of Materials Chemistry》;20070112(第17期);1326-1330 * |
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