CN109516492A - A kind of Cu2The preparation method of S micro nanocrystalline - Google Patents
A kind of Cu2The preparation method of S micro nanocrystalline Download PDFInfo
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- CN109516492A CN109516492A CN201811562431.1A CN201811562431A CN109516492A CN 109516492 A CN109516492 A CN 109516492A CN 201811562431 A CN201811562431 A CN 201811562431A CN 109516492 A CN109516492 A CN 109516492A
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- copper
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- thiocarbamide
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G3/00—Compounds of copper
- C01G3/12—Sulfides
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
Abstract
A kind of Cu2The preparation method of S micro nanocrystalline, is related to Cu2S material preparation and technical field of sewage.Copper chloride solution is made into firstly, copper chloride is dissolved in deionized water；Then, thiocarbamide is added into copper chloride solution, obtains white precipitate after ultrasound and stirring fast reaction, precipitating is filtered out just obtains copper-thiourea complex presoma；Finally, copper-thiocarbamide presoma is transferred in reaction kettle, and suitable organic solvent is added, solvothermal reaction is carried out after sealing, can be obtained Cu2S product.It is had successfully been obtained in different solvents by several Cu2The Cu for the variform that S nano structured unit is constituted2S micro nanocrystalline.This method has many advantages, such as that easy to operate, product form is controllable, visible absorption performance is excellent and low in cost.Obtain Cu2S micro nanocrystalline has good visible absorption performance, it is expected to be used for pollutant control field.
Description
Technical field
The present invention relates to Cu2S material preparation and technical field of sewage, are specifically related to a kind of Cu2S micro nanocrystalline
Preparation method.
Background technique
Vitreous copper (Cu2It S) is a kind of important mineral in nature, and a kind of important p-type semiconductor material (Eg~
1.2eV), solar battery, photoelectric device and in terms of be widely used.Usually, Cu2S nanocrystalline synthesis
And assembling is carried out in organic phase.For example, being used in the higher boilings organic phase such as lauryl amine, trioctyl phosphine oxide and oleic acid
Thermally decompose the available Cu of mercaptan acid copper presoma2S nanometer plate, nanosphere and nano wire etc..Lauryl amine, trioctyl phosphine oxide and
In the higher boilings organic phase such as oleic acid, Cu is prepared using high temperature (250~350 DEG C) means2S is nanocrystalline or quantum dot, needs
Under stringent anhydrous and oxygen free condition, preparation process is complicated, and environmental pollution is serious.
In addition, there is letter there is also being the preparation of ligand hydrothermal synthesis method with thioacetic acid, cysteine and penicillamine etc.
The advantages that list, multifunctionality, scalability, environment friendly and low cost.However, it may generally be desirable to select short chain mercaptan as
Cu2The stabilizer of S, environmental pollution is big, and the Product size obtained is small, is not readily separated.
Micro-nanometer structural material is due to larger size and stability, being easier to disperse in use and separate.
Meanwhile there are several nano structured units again in micro-nanometer structural material, therefore there are some nano effects again.Therefore, micro-nano
Advantage of the structural material with micronsize material and nano material respectively.In recent years, investigation of materials person is to various micro-nano
Structural material studies and reports that frequently with green, environmental-friendly organic solvent be reaction medium preparation.
Summary of the invention
The present invention, which is directed to, has preparation Cu2Shortcoming in the presence of S micro nanocrystalline provides a kind of Cu2S micro nanocrystalline
Preparation method.It has quickly been obtained by solvent thermal reaction with micro- in thiocarbamide-copper complex presoma and polyol medium
The Cu of nanostructure2S micro nanocrystalline.By changing the type of solvent, the Cu of different shape can get2S micro nanocrystalline.
To achieve the goals above, the technical scheme adopted by the invention is as follows: a kind of Cu2The preparation method of S micro nanocrystalline,
Firstly, by copper chloride (CuCl2·2H2O it) is dissolved in deionized water and is made into copper chloride solution；Then, by thiocarbamide (CH4N2S) add
Enter into copper chloride solution, obtains white precipitate after ultrasound and stirring fast reaction, precipitating is filtered out just obtain copper-sulphur
Urea complex precursors；Finally, copper-thiocarbamide presoma is transferred in reaction kettle, and suitable organic solvent is added, after sealing
Solvothermal reaction is carried out, can be obtained Cu2S product.
As the optimal technical scheme of preparation method of the present invention, copper chloride and thiocarbamide adds when preparing copper-thiocarbamide presoma
Dosage molar ratio is 1.5~3:1, and the reaction time is 1~10min.Solvothermal adds when reacting to every 1g copper-thiocarbamide presoma
Enter the ethylene glycol or glycerine of 5~20mL.The micromorphology that product is prepared when organic solvent is ethylene glycol is to be assembled by nanometer sheet
Made of micron club shaped structure；It is micro- to be assembled by nanometer sheet that the micromorphology of product is prepared when organic solvent is glycerine
Rice chondritic.Solvothermal reaction reaction temperature be 180~200 DEG C, the reaction time be 6~for 24 hours.
Compared with prior art, beneficial effects of the present invention are shown:
The present invention is had successfully been obtained in different solvents using copper-thiourea complex as presoma by several Cu2S nano junction
The Cu for the variform that structure unit is constituted2S micro nanocrystalline.This method is with easy to operate, product form is controllable, visible absorption
The advantages that haveing excellent performance and be low in cost.Obtain Cu2S micro nanocrystalline has good visible absorption performance, it is expected to for dirt
It contaminates object and administers field.
Detailed description of the invention
Fig. 1 is the XRD diagram that two kinds of form micro nanocrystalline products are prepared in embodiment 1；
Fig. 2 a, b be in embodiment 1 by ethylene glycol be organic solvent preparation micro nanocrystalline product in the form of and chemical composition；
Fig. 2 c, d be in embodiment 1 by glycerine be organic solvent preparation micro nanocrystalline product in the form of and chemical composition；
Fig. 3 be embodiment 1 in using ethylene glycol, glycerine as the obtained micro nanocrystalline of organic solvent wavelength and band gap
The relation curve of size；
Fig. 4 is the form that the differential responses time prepares micro nanocrystalline product in embodiment 2.
Specific embodiment
With reference to embodiments with attached drawing to Cu of the invention2The preparation method of S micro nanocrystalline, which is made, to be discussed further.
Structure, the form performance of the method for the present invention products therefrom be respectively adopted field emission scanning electron microscope (FE-SEM, SU8010),
X-ray powder diffraction (XRD, D3500) and ultraviolet-visible spectrometer (Vb300) are characterized and are analyzed.
Embodiment 1:
A kind of Cu2The preparation method of S micro nanocrystalline, steps are as follows:
1), by the copper chloride (CuCl of 17g2·2H2O it) is dissolved in the deionized water of 100mL and is made into copper chloride solution.
2), by the thiocarbamide (CH of 4g4N2S it) is added into above-mentioned copper chloride solution, after ultrasound and the quick 5min reaction of stirring
White precipitate is obtained, precipitating is filtered out just obtains copper-thiourea complex presoma.
3) it, takes copper-thiocarbamide presoma of 10g to be transferred in reaction kettle, and the organic solvent of 100mL is added, seal laggard
Row solvothermal reacts (180 DEG C, 18h), can be obtained Cu2S product.
Above-mentioned organic solvent selects ethylene glycol and glycerine respectively, by selection differential responses medium type observation to Cu2S
The influence of structure, form and optical property.
Fig. 1 be embodiment 1 in prepare two kinds of form micro nanocrystalline products XRD diagram (a, b respectively correspond organic solvent selection
Ethylene glycol, glycerine prepare product), as can be seen that the product of two kinds of forms is high-purity compared with standard x RD spectrogram
Cu2S object phase.
Fig. 2 a, b be in embodiment 1 by ethylene glycol be organic solvent preparation micro nanocrystalline product in the form of and chemical composition,
By figure as can be seen that using ethylene glycol to carry out solvothermal reaction as solvent prepares the micromorphology of product as by nanometer
The micron club shaped structure that piece assembles, each lamellar spacing are 60nm or so.Fig. 2 b is to take local distribution, and Cu and S are in standard
The ratio between diffraction maximum of spectrum is 2:1.
Fig. 2 c, d be in embodiment 1 by glycerine be organic solvent preparation micro nanocrystalline product in the form of and chemical composition,
By figure as can be seen that using glycerine to carry out solvothermal reaction as solvent prepares the micromorphology of product as by nanometer
The micron chondritic that piece assembles, partial size is than more uniform.Fig. 2 d is to take local distribution, the diffraction maximum of Cu and S in standard spectrum
The ratio between be 2:1.
Fig. 3 be embodiment 1 in using ethylene glycol, glycerine as the obtained micro nanocrystalline of organic solvent wavelength and band gap
The relation curve of size, as seen in Figure 3 rodlike and spherical Cu2The maximum absorption wavelength of S almost all in 500nm, into
One step is estimated that the band gap of the two may each be about 1.24eV.
Embodiment 2: the reaction time is to Cu2The influence of S micro nanocrystalline form.
The preparation method is the same as that of Example 1, under the premise of using glycerine as reaction dissolvent, respectively react 6h, 12h, 18h,
For 24 hours, the Cu of tetra- kinds of corresponding Fig. 4 a, Fig. 4 b, Fig. 4 c, Fig. 4 d different-shapes is obtained2S micro nanocrystalline product.
As seen in Figure 4, products therefrom (Fig. 4 a, b) is different when reacting 6h and 12h；When being reacted to 18h or so
When obtained product (Fig. 4 c) distributional pattern different, different by initial shape size gradually become spherical distribution；
Products therefrom (Fig. 4 d) sphericity is higher after reacting for 24 hours, distribution uniform.But under the reaction time is too long, nano ply accumulation
Cu2It will appear hollow phenomenon when S microballoon.
The above content is just an example and description of the concept of the present invention, affiliated those skilled in the art
It makes various modifications or additions to the described embodiments or is substituted in a similar manner, without departing from invention
Design or beyond the scope defined by this claim, be within the scope of protection of the invention.
Claims (5)
1. a kind of Cu2The preparation method of S micro nanocrystalline, which is characterized in that firstly, by copper chloride (CuCl2·2H2O) be dissolved in from
Copper chloride solution is made into sub- water；Then, by thiocarbamide (CH4N2S it) is added into copper chloride solution, ultrasound and stirring are quick
White precipitate is obtained after reaction, precipitating is filtered out just obtains copper-thiourea complex presoma；Finally, by copper-thiocarbamide forerunner
Body is transferred in reaction kettle, and suitable organic solvent is added, and solvothermal reaction is carried out after sealing, can be obtained Cu2S is produced
Object.
2. preparation method as described in claim 1, which is characterized in that copper chloride and thiocarbamide when preparing copper-thiocarbamide presoma
Additive amount molar ratio is 1.5~3:1, and the reaction time is 1~10min.
3. preparation method as described in claim 1, which is characterized in that every 1g copper-thiocarbamide forerunner when solvothermal reacts
The ethylene glycol or glycerine of 5~20mL is added in body.
4. preparation method as claimed in claim 3, which is characterized in that organic solvent prepares the microcosmic shape of product when being ethylene glycol
State is the micron club shaped structure assembled by nanometer sheet；The micromorphology that product is prepared when organic solvent is glycerine is by receiving
The micron chondritic that rice piece assembles.
5. preparation method as described in claim 1, which is characterized in that the reaction temperature of solvothermal reaction is 180~200
DEG C, the reaction time be 6~for 24 hours.
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Cited By (4)
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| CN110683571A (en) * | 2019-09-27 | 2020-01-14 | 中国科学院合肥物质科学研究院 | Preparation method of flower-shaped cuprous sulfide micron particles |
| CN110777449A (en) * | 2019-11-20 | 2020-02-11 | 电子科技大学 | Porous Cu 7S 4/Cu(OH) 2Composite nanofiber material and preparation method thereof |
| CN110980795A (en) * | 2019-11-20 | 2020-04-10 | 江苏大学 | Hydrothermal method for preparing Cu2-xMethod for preparing S nanoflower and application of S nanoflower to near-infrared photothermal material |
| CN111333100A (en) * | 2020-03-20 | 2020-06-26 | 东华大学 | Preparation method of copper sulfide particle crystal form |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110683571A (en) * | 2019-09-27 | 2020-01-14 | 中国科学院合肥物质科学研究院 | Preparation method of flower-shaped cuprous sulfide micron particles |
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| CN110777449A (en) * | 2019-11-20 | 2020-02-11 | 电子科技大学 | Porous Cu 7S 4/Cu(OH) 2Composite nanofiber material and preparation method thereof |
| CN110980795A (en) * | 2019-11-20 | 2020-04-10 | 江苏大学 | Hydrothermal method for preparing Cu2-xMethod for preparing S nanoflower and application of S nanoflower to near-infrared photothermal material |
| CN110777449B (en) * | 2019-11-20 | 2021-03-30 | 电子科技大学 | Porous Cu7S4/Cu(OH)2Composite nanofiber material and preparation method thereof |
| CN111333100A (en) * | 2020-03-20 | 2020-06-26 | 东华大学 | Preparation method of copper sulfide particle crystal form |
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