CN102040239B - Preparation method of submicron CuS (copper sulphide) classification ball - Google Patents
Preparation method of submicron CuS (copper sulphide) classification ball Download PDFInfo
- Publication number
- CN102040239B CN102040239B CN2011100209776A CN201110020977A CN102040239B CN 102040239 B CN102040239 B CN 102040239B CN 2011100209776 A CN2011100209776 A CN 2011100209776A CN 201110020977 A CN201110020977 A CN 201110020977A CN 102040239 B CN102040239 B CN 102040239B
- Authority
- CN
- China
- Prior art keywords
- preparation
- solution
- classification
- cupric sulfide
- copper
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Images
Abstract
The invention discloses a preparation method of submicron CuS (copper sulphide) classification balls. The method comprises the following steps: adding polymer into a good solvent to dissolve and remove big gel particles; adding copper source solution to the good solvent and stirring; adding sulfur source solution and then stirring; reacting the reaction liquid under 100-1,000 KPa at 100-200 DEG C; naturally cooling to the room temperature to obtain black precipitate; and washing and drying the precipitate to obtain the classification balls. The classification balls has the advantages of cheap and readily available templates, environmental friendliness, safety without toxicity, renewability and high water solubility, the contents of raw materials are abundant in nature and the operation of the reaction system is simple; the size and structure of the prepared classification ball are adjustable: the diameter can be controlled by adjusting the molar weight of the added precursor, the template concentration, the reaction temperature and time and the like; the operation is simple; and the prepared classification balls have wide application value in the fields of catalyst, catalyst carrier, optical equipment, sensor, lithium-ion rechargeable battery cathode material, superconductor and the like.
Description
Technical field
The present invention relates to inorganic nano material and field of functional materials, particularly a kind of is the method that template prepares submicron order CuS classification ball with the polymkeric substance.
Background technology
Cupric sulfide (CuS) nanoparticle is a kind of P-type semiconductor; It has the following advantages: (1) has that good visible absorption, infrared region see through, pl-and big optical characteristics such as non-linear susceptibility, has the potential using value in fields such as novel light shutter device, photocatalyst and optoelectronic poles; (2) have the characteristic of high conductivity and high-energy capacitor, so be cathode material good in the lithium ion battery; (3) when temperature equals 1.6K, show good superconducting property, therefore, it still is good low temperature superconducting material.In addition, it also can be used as high temperature fast ion conducting material, nanometer photoswitch etc.The physics of copper sulphide nano particles and chemical property and its form and size are closely related, and the cupric sulfide that therefore prepares different shape has good theory significance and researching value to improving its physicochemical property.
The physicochemical property of cupric sulfide and its size and form have confidential relation, so preparation morphological structure and size control become the focus of Recent study.At present, people have prepared the cupric sulfide of different dimensions and form.For example: copper sulfide nano rice noodles, copper sulfide nano mitron, copper sulphide nano rod, copper sulphide nano dish, hollow cupric sulfide microballoon, hollow cupric sulfide cubes etc.The Chinese patent publication number is that CN1958459 has introduced the preparation of hexagonal Nano slices of copper sulphide (dish).The contriver is a tensio-active agent with chain alkyl amine, is the sulphur source with dithiocarbonic anhydride, is reaction solvent with toluene, adopts the chemical solution method preparation to have the Nano slices of copper sulphide (dish) of the hexagonal configuration of rule.At first mantoquita, sulphur source and chain alkyl amine are dissolved in the toluene, preparation feedback liquid carries out solvent heat treatment with the reaction solution for preparing then, controlled temperature and reaction times, can obtain the regular hexagonal Nano slices of copper sulphide (dish) of pattern.About 26 ± the 1.5nm of diameter of the cupric sulfide hexagonal nanometer sheet (dish) for preparing by this method, the about 8 ± 1.2nm of thickness, and also this hexagonal nanometer sheet can be self-assembled into column, raft shape, lamellated nano-superstructure.Chinese patent number is 200610042896 to disclose a kind of preparation of monodisperse copper sulfide semiconductor nano particles.This preparation method is with common mantoquita, sodium sulphite and N, and N-dialkyl dithio formate is a raw material, has made monodisperse copper sulfide semiconductor nano particles through easy chemical reaction reagent.Chinese patent number is that 200610010288 to disclose the shape control of copper sulphide nano structure synthetic, and this invention can improve the controllability of its productive rate and implementation structure through the synthesis temperature of adjusting cupric sulfide.Chinese patent number is 200510111375 to have invented through reaction in microemulsion and synthesized star shaped copper sulfide.This invention is a template with the microemulsion that novel quaternary ammonium salt cationic Gemini tensio-active agent forms, and has made the star shaped copper sulfide of narrow size distribution through control emulsion synthesis condition, spinning, drying.Prepared star shaped copper sulfide has widely at aspects such as the color indicator of pigment, catalyzer, nigrosine, semiconductor materials to be used.Chinese patent number is 200510103028 to disclose metals ion and sulfocompound are reacted in the mixed system of alkali metal hydroxide, lipid acid and organic polar solvent, obtains sulfide nano-particle.It is raw material that the present invention adopts inorganic salt, alkali metal hydroxide, sulfocompound; In the mixed system of lipid acid, water, organic polar solvent, react; Promptly can obtain the sulfide particles of dispersed nano level, prepared sulfide nano-particle is widely used in fields such as biomarker, analysis and solar cells.Chinese patent number is 200710013063 to disclose the preparation method of cupric sulfide hollow ball; Earlier with a certain amount of metallic copper soluble salt and Vinylpyrrolidone polymer (PVP) the formation clear soln that is dissolved in the water; Add a certain amount of reductive agent then, obtain yellow-orange suspension; Adding a certain amount of sulphur source material and control reaction temperature again is promptly to make the cupric sulfide hollow ball in 10 minutes to 24 hours at 10-90 ℃, reaction times.In addition, Chinese patent number is 200910050776 to disclose the preparation of nano-copper sulfide matrix material, has opened up the Application Areas of cupric sulfide.
There is following shortcoming in the preparation method of above different shape structure cupric sulfide: (1) employed organic solvent has bigger toxicity, to environment protection and healthy unfavorable; (2) synthesis condition requires harsh; (3) complicated operation; (4) classification globosity cupric sulfide is difficult for reaching.In a word, above method is difficult to realize simultaneously that form and controllable size and environmental friendliness prepare the difficult problem of cupric sulfide, thus invent that a kind of process is comparatively simple, environmental friendliness, classification globosity preferably the preparation method of copper sulphide nano structure seem very important.
Summary of the invention
The objective of the invention is to overcome shortcoming of the prior art; Provide that a kind of raw material is easy to get, technology is simple, environmental friendliness, method safe and efficient, that be convenient to promote prepare submicron order cupric sulfide classification ball; Submicron order cupric sulfide classification ball preparation method provided by the invention is template with the polymkeric substance, and reaction realizes in single aqueous systems.
The object of the invention is realized through following technology:
A kind of preparation method of submicron order cupric sulfide classification ball; Be to be template with the polymkeric substance; React in the solution that the precursor and the sulphur source of copper joined polymkeric substance successively,, specifically comprise the steps: making submicron order cupric sulfide classification ball through low-temperature hydrothermal, washing, drying
(1) preparation of polymer template: polymkeric substance is added in the good solvent; At 25-100 ℃ of heating for dissolving 0.5-1h, be mixed with the solution of 0.1-0.5wt.%, be cooled to room temperature after; Freezing down at 4-8 ℃; The centrifugal 3-20min of 3500-8000rpm then, frozen centrifugation is removed for 2-5 time behind the big gel particle as the storing solution use so repeatedly, and the diameter of the polymer template that makes is 100-1000nm;
Said good solvent is water, DMSO 99.8MIN. (DMSO), acetone (actone), N, any one in the dinethylformamide (DMF).
(2) preparation in copper source: the solution for standby that soluble copper salt is mixed with 0.01-1mol/L;
(3) preparation in sulphur source: the solution for standby that the solubility sulfocompound is mixed with 0.01-1mol/L;
(4) get the prepared template solution of a certain amount of step (1) in container; In 30-90 ℃ of heated and stirred, then, with the quick adding of the copper source solution of step (2) preparation wherein; Add-on is the 0.2%-35% of template solution volume, continues to stir 0.5-24h down at 30-90 ℃;
(5) the sulphur source solution of step (3) preparation is joined in the reaction solution that step (4) obtains, add-on is the 0.4%-52% of template solution volume, continues to stir 2-24h down at 30-90 ℃;
(6) reaction solution that step (5) is obtained is under 100KPa-1000KPa pressure, and 100-200 ℃ of reaction 1min-48h naturally cools to room temperature and obtain black precipitate;
(7) black precipitate that step (6) is obtained is washed 3-10 time respectively with 70-100 ℃ deionized water and absolute ethyl alcohol;
(8) the black cupric sulfide powder of step (7) washing purifying being crossed promptly gets submicron order cupric sulfide classification ball in 50-100 ℃ of dry 1-24h.
Said polymkeric substance comprises chitosan, Zulkovsky starch for adopting the polyose of natural matter preparation.
The weight-average molecular weight of said polyose is 1000-100000.
Said soluble copper salt is any one in cupric chloride, copper sulfate, cupric nitrate, the neutralized verdigris.
Said solubility sulfocompound is any one in Sulfothiorine, sodium sulphite, potassium sulphide, thiocarbamide, the dithiocarbonic anhydride.
The submicron order cupric sulfide classification ball that method for preparing obtains is assembled by the copper sulphide nano small-particle of 10-30nm and is formed, and the diameter of the cupric sulfide classification ball of being formed is about 100-500nm.
The present invention compared with prior art has following advantage and effect:
(1) to adopt the polymkeric substance of commercial obtainable natural material preparation be that template has tangible advantage in the present invention, and at first, this template is cheap and easy to get, environmental friendliness, safety non-toxic, renewable, good water solubility, starting material nature content are abundant; Secondly, compare with common small molecules tensio-active agent with the synthetic polymkeric substance, reaction system is simple to operate; At last, this natural polymer template is prone to remove, and energy consumption is low;
(2) size and the Adjustable structure of the submicron order cupric sulfide classification ball of the present invention's preparation: diameter can add the molar weight of precursor, the concentration of template, the controls such as temperature and time of reaction through adjusting, and is simple to operate.
(3) the present invention utilizes natural polymer to enrich the natural polymer theory that inorganic precursor is assembled the classification ball for soft template leads for template assembling submicron order cupric sulfide classification ball, for the assembling of studying classification balls such as other MOX, metallic sulfide, metal is laid a good foundation.
(4) the submicron order cupric sulfide classification ball of the present invention's preparation is with a wide range of applications in Application Areass such as catalyzer, support of the catalyst, optical device, transmitter, lithium ion chargeable battery cathode material, superconductors.
(5) technological process of the present invention is simple, and plant and instrument is cheap, and reaction conditions is gentle, and energy consumption is low, safety non-pollution, and productive rate is high, and is applied widely, is convenient to large-scale industrial production, has feasibility preferably.
Description of drawings
Fig. 1 is the transmission electron microscope photo of the starch gel of absorption bivalent cupric ion
Fig. 2 is the transmission electron microscope photo of the submicron order cupric sulfide classification ball of 100 ℃ of hydro-thermal 1min preparations
Fig. 3 is the transmission electron microscope photo of the submicron order cupric sulfide classification ball of 100 ℃ of hydro-thermal 24h preparations
Fig. 4 is the infrared spectrogram of the submicron order cupric sulfide classification ball of 100 ℃ of hydro-thermal 24h preparations
Fig. 5 is the uv absorption spectra of the submicron order cupric sulfide classification ball of 100 ℃ of hydro-thermal 24h preparations
Embodiment
Below in conjunction with embodiment and accompanying drawing the present invention is done further detailed description, but embodiment of the present invention is not limited thereto.
Embodiment one
A. the preparation of chitosan template: W-Gum (purchasing spy's chemical ltd in Rui Jin, Tianjin) is dissolved in DMSO,, is mixed with the solution of 0.25wt.% at 95 ℃ of heating for dissolving 0.5h.Be cooled to and put into 4 ℃ of refrigerator and cooled after the room temperature and freeze, the centrifugal 15min of 4000rpm then, frozen centrifugation is removed for 3 times behind the big gel particle practical as storing solution so repeatedly;
B. the preparation in copper source: take by weighing the solution for standby that cupric chloride is mixed with 0.5M;
C. the preparation in sulphur source: take by weighing the solution for standby that Sulfothiorine is mixed with 0.5M;
Get 18.4mL, the corn starch solution of 0.25wt% stirs in 70 ℃ of oil baths; Then, with 0.8mL, the Cupric Chloride Solution of 0.5M joins and stirs 30min in the corn starch solution; Obtain a clear solution azury, the transmission electron microscope photo of clear solution is as shown in Figure 1, and the diameter that records template is D==766 ± 147nm; With 0.8mL, 0.5M Sulfothiorine adds reaction fast again, obtains the suspension-s of a black behind 70 ℃ of heated and stirred 2h; Again this suspension-s is transferred in the reaction kettle in pressure 150KPa, 100 ℃ of hydro-thermal 24h, the transmission electron microscope photo of hydro-thermal 1min reaction solution is as shown in Figure 2; Can be known by Fig. 2: the diameter of the submicron order cupric sulfide classification ball of gained is D=224 ± 47nm, and this classification ball was formed by brilliant gathering of little copper sulphide nano.The transmission electron microscope photo of hydro-thermal 24h reaction solution is as shown in Figure 3, can be known by Fig. 3: the diameter of the submicron order cupric sulfide classification ball of gained is D=362 ± 27nm, and along with the prolongation of time, the classification ball denser that becomes.Then reaction solution is naturally cooled to room temperature, the black precipitate that obtains is washed respectively 3 times with 80-90 ℃ zero(ppm) water and absolute ethyl alcohol,, promptly obtain submicron order cupric sulfide classification ball, productive rate 95.6% again at 60 ℃ of dry 10h.The infrared spectrogram of submicron order cupric sulfide classification ball is as shown in Figure 4.Can be known by Fig. 4: prepared submicron order cupric sulfide classification ball has infrared light perviousness preferably.The uv absorption spectra of submicron order cupric sulfide classification ball is as shown in Figure 5.The diameter that can be known submicron order cupric sulfide classification ball by Fig. 5 is D=362 ± 27nm, and this classification microballoon has absorption at 375.5nm and 681.5nm place respectively, is different from the cupric sulfide of other forms and size.
Embodiment 2
A. the preparation of chitosan template: chitosan (purchasing spy's chemical ltd in Rui Jin, Tianjin) is dissolved in deionized water; At 25 ℃ of heating for dissolving 1h; Be mixed with the solution of 0.1wt.%; Be cooled to and put into 8 ℃ of refrigerator and cooled after the room temperature and freeze, the centrifugal 20min of 3500rpm then, frozen centrifugation is removed for 2 times behind the big gel particle practical as storing solution so repeatedly;
B. the preparation in copper source: take by weighing the solution for standby that cupric nitrate is mixed with 0.01M;
C. the preparation in sulphur source: take by weighing the solution for standby that sodium sulphite is mixed with 0.01M;
Get 18.4mL, the chitosan solution of 0.1wt% stirs in 30 ℃ of oil baths; Then, with 0.0368mL, the Cupric Chloride Solution of 0.01M joins and stirs 24min in the chitosan solution; Obtain a clear solution azury, again with 0.0736mL, 0.01M Sulfothiorine adds reaction fast; Obtain the suspension-s of a black behind 30 ℃ of heated and stirred 24h, again this suspension-s is transferred in the reaction kettle in pressure 200KPa 200 ℃ of hydro-thermal 1min.Naturally cool to room temperature; The black precipitate that obtains is washed respectively 3 times with 70-80 ℃ deionized water and absolute ethyl alcohol; At 50 ℃ of dry 24h, promptly obtain submicron order cupric sulfide classification ball, productive rate 95.6% again; The copper sulphide nano small particle diameters is 10-20nm, and the diameter of the cupric sulfide classification ball of being formed is 200-300nm.
Embodiment 3
A. the preparation of W-Gum template: (the special chemical in Rui Jin, Tianjin ltd) is dissolved in acetone with W-Gum, at 100 ℃ of heating for dissolving 0.5h, is mixed with the solution of 0.5wt.%.Be cooled to and put into refrigerator and cooled after the room temperature and freeze, the centrifugal 3min of 8000rpm then, frozen centrifugation is removed for 5 times behind the big gel particle practical as storing solution so repeatedly;
B. the preparation in copper source: take by weighing the solution for standby that neutralized verdigris is mixed with 1M;
C. the preparation in sulphur source: take by weighing the solution for standby that potassium sulphide is mixed with 1M;
Get the 18.4mL corn starch solution, in 90 ℃ of oil baths, stir, then; With 6.44mL, the Cupric Chloride Solution of 1M joins and stirs 30min in the corn starch solution, obtains a clear solution azury; With 9.568mL, 0.1M Sulfothiorine adds reaction fast again, obtains the suspension-s of a black behind 90 ℃ of heated and stirred 2h; Again this suspension-s is transferred in the reaction kettle in pressure 200KPa 100 ℃ of hydro-thermal 48h.Naturally cool to room temperature; The black precipitate that obtains is washed respectively 5 times with 75-80 ℃ zero(ppm) water and absolute ethyl alcohol; At 100 ℃ of dry 1h, promptly obtain submicron order cupric sulfide classification ball, productive rate 98.1% again; The copper sulphide nano small particle diameters is 80-85nm, and the diameter of the cupric sulfide classification ball of being formed is 900-1000nm.
Embodiment 4
A. the preparation of potato starch template: (the special chemical in Rui Jin, Tianjin ltd .) is dissolved in N with potato starch, and dinethylformamide at 95 ℃ of heating for dissolving 0.5h, is mixed with the solution of 0.25wt.%.Be cooled to and put into refrigerator and cooled after the room temperature and freeze, the centrifugal 10min of 4000rpm then, frozen centrifugation is removed for 3 times behind the big gel particle practical as storing solution so repeatedly;
B. the preparation in copper source: take by weighing the solution for standby that cupric nitrate is mixed with 0.5M;
C. the preparation in sulphur source: take by weighing the solution for standby that thiocarbamide is mixed with 0.5M
Get 20mL potato starch solution, in 60 ℃ of oil baths, stir, then; With 2mL, the copper nitrate solution of 0.5M joins in the potato starch solution and stirs 12h, obtains a clear solution azury; With 2mL, 0.5M sodium sulphite adds reaction fast again, obtains the suspension-s of a black behind 60 ℃ of heated and stirred 2h; Again this suspension-s is transferred in the reaction kettle in pressure 300KPa 100 ℃ of hydro-thermal 12h.Naturally cool to room temperature; The black precipitate that obtains is washed respectively 6 times with the zero(ppm) water and the absolute ethyl alcohol of heat; At 80 ℃ of dry 6h, promptly obtain submicron order cupric sulfide classification ball, productive rate 91.2% again; The copper sulphide nano small particle diameters is 20-30, and the diameter of the cupric sulfide classification ball of being formed is 700-850nm.
Embodiment 5
A. the preparation of starch template: W-Gum (purchasing spy's chemical ltd in Rui Jin, Tianjin) is dissolved in N, and dinethylformamide at 95 ℃ of heating for dissolving 0.5h, is mixed with the solution of 0.5wt.%.Be cooled to and put into refrigerator and cooled after the room temperature and freeze, the centrifugal 15min of 4000rpm then, frozen centrifugation is removed for 3 times behind the big gel particle practical as storing solution so repeatedly;
B. the preparation in copper source: take by weighing the solution for standby that copper sulfate is mixed with 0.5M;
C. the preparation in sulphur source: take by weighing the solution for standby that thiocarbamide is mixed with 0.5M;
Get the 18.4mL corn starch solution, in 70 ℃ of oil baths, stir, then; With 3.68mL, the copper-bath of 0.5M joins and stirs 30min in the starch solution, obtains a clear solution azury; With 3.68mL, the 0.5M thiocarbamide adds reaction fast again, obtains the suspension-s of a black behind 70 ℃ of heated and stirred 2h; Again this suspension-s is transferred in the reaction kettle in pressure 500KPa 100 ℃ of hydro-thermal 24h.Naturally cool to room temperature; The black precipitate that obtains is washed respectively 3 times with the zero(ppm) water and the absolute ethyl alcohol of heat; At 60 ℃ of dry 10h, promptly obtain submicron order cupric sulfide classification ball, productive rate 93.5% again; The copper sulphide nano small particle diameters is 15-20nm, and the diameter of the cupric sulfide classification ball of being formed is 250-300nm.
Embodiment 6
A. the preparation of potato starch template: potato starch (purchasing spy's chemical ltd in Rui Jin, Tianjin) is dissolved in N, and dinethylformamide at 95 ℃ of heating for dissolving 0.5h, is mixed with the solution of 0.3wt.%.Be cooled to and put into refrigerator and cooled after the room temperature and freeze, the centrifugal 15min of 4000rpm then so removes for 3 times behind the big gel particle practical as storing solution repeatedly;
B. the preparation in copper source: take by weighing the solution for standby that cupric chloride is mixed with 0.5M;
C. the preparation in sulphur source: take by weighing the solution for standby that dithiocarbonic anhydride is mixed with 0.5M;
Get 9.2mL potato starch solution, in 60 ℃ of oil baths, stir, then; With 2.76mL, the Cupric Chloride Solution of 0.5M joins and stirs 30min in the starch solution, obtains a clear solution azury; With 2.76mL, 0.5M Sulfothiorine adds reaction fast again, obtains the suspension-s of a black behind 60 ℃ of heated and stirred 2h; Again this suspension-s is transferred in the reaction kettle in pressure 200KPa 180 ℃ of hydro-thermal 16h.Naturally cool to room temperature; The black precipitate that obtains is washed respectively 3 times with 85 ℃ zero(ppm) water and absolute ethyl alcohol; At 100 ℃ of dry 2h, promptly obtain submicron order cupric sulfide classification ball, productive rate 97.3% again; The copper sulphide nano small particle diameters is 30-400nm, and the diameter of the cupric sulfide classification ball of being formed is 150-200nm.
Embodiment 7
A. the preparation of W-Gum template: W-Gum (purchasing spy's chemical ltd in Rui Jin, Tianjin) is dissolved in DMSO 99.8MIN.,, is mixed with the solution of 0.15wt.% at 100 ℃ of heating for dissolving 0.5h.Be cooled to and put into refrigerator and cooled after the room temperature and freeze, the centrifugal 15min of 4000rpm then, frozen centrifugation is removed for 3 times behind the big gel particle practical as storing solution so repeatedly;
B. the preparation in copper source: take by weighing the solution for standby that copper sulfate is mixed with 0.6M;
C. the preparation in sulphur source: take by weighing the solution for standby that Sulfothiorine is mixed with 0.6M;
Get the 20mL corn starch solution, in 80 ℃ of oil baths, stir, then; With 6mL, the copper-bath of 0.6M joins and stirs 24h in the corn starch solution, obtains a clear solution azury; With 8mL, 0.6M Sulfothiorine adds reaction fast again, obtains the suspension-s of a black behind 80 ℃ of heated and stirred 2h; Again this suspension-s is transferred in the reaction kettle in pressure 1000KPa 110 ℃ of hydro-thermal 24h.Naturally cool to room temperature; The black precipitate that obtains is washed respectively 3 times with 100 ℃ zero(ppm) water and absolute ethyl alcohol; At 60 ℃ of dry 10h, promptly obtain submicron order cupric sulfide classification ball, productive rate 95.6% again; The copper sulphide nano small particle diameters is 20-30nm, and the diameter of the cupric sulfide classification ball of being formed is 300-400nm.
Above embodiment is preferred implementation of the present invention; But embodiment of the present invention is not restricted to the described embodiments; Other any do not deviate from change, the modification done under spirit of the present invention and the principle, substitutes, combination, simplify; All should be the substitute mode of equivalence, be included within protection scope of the present invention.
Claims (4)
1. the preparation method of a submicron order cupric sulfide classification ball is characterized in that may further comprise the steps:
(1) preparation of polymer template: polymkeric substance is added in the good solvent; At 25-100 ℃ of heating for dissolving 0.5-1h; Be mixed with the solution of 0.1-0.5wt.%, be cooled to room temperature after, down freezing at 4-8 ℃; The centrifugal 3-20min of 3500-8000rpm then, so frozen centrifugation uses as storing solution after removing big gel particle for 2-5 time repeatedly;
Said polymkeric substance is the polyose of natural matter preparation; Said polyose is chitosan or Zulkovsky starch; Said good solvent is water, DMSO 99.8MIN., acetone, N, any one in the dinethylformamide;
(2) preparation in copper source: the solution for standby that soluble copper salt is mixed with 0.01-1mol/L;
(3) preparation in sulphur source: the solution for standby that the solubility sulfocompound is mixed with 0.01-1mol/L;
(4) get the prepared template solution of a certain amount of step (1) in container; In 30-90 ℃ of heated and stirred, then, with the quick adding of the copper source solution of step (2) preparation wherein; Add-on is the 0.2%-35% of template solution volume, continues to stir 0.5-24h down at 30-90 ℃;
(5) the sulphur source solution of step (3) preparation is joined in the reaction solution that step (4) obtains, add-on is the 0.4%-52% of template solution volume, continues to stir 2-24h down at 30-90 ℃;
(6) reaction solution that step (5) is obtained is under 100kPa-1000kPa pressure, and 100-200 ℃ of reaction 1min-48h naturally cools to room temperature and obtain black precipitate;
(7) black precipitate that step (6) is obtained is washed 3-10 time respectively with 70-100 ℃ deionized water and absolute ethyl alcohol;
(8) the black cupric sulfide powder of step (7) washing purifying being crossed promptly gets submicron order cupric sulfide classification ball in 50-100 ℃ of dry 1-24h.
2. according to the preparation method of the said a kind of submicron order cupric sulfide classification ball of claim 1, it is characterized in that: the weight-average molecular weight of said polyose is 1000-100000.
3. according to the preparation method of the said a kind of submicron order cupric sulfide classification ball of claim 1, it is characterized in that: said soluble copper salt is any one in cupric chloride, copper sulfate, cupric nitrate, the neutralized verdigris.
4. according to the preparation method of the said a kind of submicron order cupric sulfide classification ball of claim 1, it is characterized in that: said solubility sulfocompound is any one in Sulfothiorine, sodium sulphite, potassium sulphide, thiocarbamide, the dithiocarbonic anhydride.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2011100209776A CN102040239B (en) | 2011-01-18 | 2011-01-18 | Preparation method of submicron CuS (copper sulphide) classification ball |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2011100209776A CN102040239B (en) | 2011-01-18 | 2011-01-18 | Preparation method of submicron CuS (copper sulphide) classification ball |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102040239A CN102040239A (en) | 2011-05-04 |
| CN102040239B true CN102040239B (en) | 2012-05-30 |
Family
ID=43906832
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2011100209776A Expired - Fee Related CN102040239B (en) | 2011-01-18 | 2011-01-18 | Preparation method of submicron CuS (copper sulphide) classification ball |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102040239B (en) |
Families Citing this family (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102795655B (en) * | 2012-07-30 | 2015-04-08 | 黑龙江大学 | Method for preparing hierarchical floriform hollow-structure CuS |
| CN102863006A (en) * | 2012-09-25 | 2013-01-09 | 镇江市高等专科学校 | Preparation method of copper sulfide ultra-long micro-wire |
| CN102910667A (en) * | 2012-10-23 | 2013-02-06 | 中科院广州化学有限公司 | Hydrophilic vermiform CuS (copper sulphide) agglomerate and preparation method and usage thereof |
| CN103145173B (en) * | 2013-03-06 | 2014-12-24 | 浙江大学 | Preparation method of copper sulphide classified nanometer structure material |
| CN103232058A (en) * | 2013-05-16 | 2013-08-07 | 东华大学 | Method for preparing copper sulphide/graphene nano-composite material |
| CN104609457B (en) * | 2015-02-11 | 2016-11-02 | 东南大学 | The preparation method and applications of overstable copper sulphide nano bunch |
| CN107673396B (en) * | 2017-11-19 | 2019-02-26 | 江西理工大学 | A kind of preparation method of high-purity cuprous sulfide |
| CN108940376B (en) * | 2018-07-25 | 2021-06-25 | 广州大学 | Surface organic complexing copper sulfide Fenton catalyst and synthetic method and application thereof |
| CN110395759B (en) * | 2019-08-06 | 2021-04-13 | 西安交通大学 | Preparation method of copper sulfide nanoflower |
| CN112366312B (en) * | 2020-10-19 | 2021-10-08 | 杭州职业技术学院 | Carbon-assembled zinc sulfide hollow nano polyhedral honeycomb material and preparation and application thereof |
| CN112366298B (en) * | 2020-10-19 | 2021-10-08 | 杭州职业技术学院 | Carbon-assembled zinc sulfide cobalt sulfide hollow nano polyhedral framework material and preparation and application thereof |
| CN112279293B (en) * | 2020-11-02 | 2023-08-25 | 贵州理工学院 | Preparation method of copper sulfide nano material |
| CN112891618B (en) * | 2021-01-28 | 2022-06-21 | 浙江大学 | In-situ photocuring antibacterial bone defect repair gel and preparation method thereof |
| CN113860355B (en) * | 2021-10-28 | 2023-04-25 | 武汉大学 | Preparation method and application of beaded copper sulfide particles |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101391199A (en) * | 2007-09-21 | 2009-03-25 | 中国科学院化学研究所 | Multi-cavity composite micro/nano capsule and preparation method and device thereof |
| CN101851010A (en) * | 2010-06-08 | 2010-10-06 | 南开大学 | Synthesizing method for transition metal sulfide |
-
2011
- 2011-01-18 CN CN2011100209776A patent/CN102040239B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101391199A (en) * | 2007-09-21 | 2009-03-25 | 中国科学院化学研究所 | Multi-cavity composite micro/nano capsule and preparation method and device thereof |
| CN101851010A (en) * | 2010-06-08 | 2010-10-06 | 南开大学 | Synthesizing method for transition metal sulfide |
Non-Patent Citations (1)
| Title |
|---|
| Minmin Li et al..A simple route to synthesize CuS framework with porosity.《Journal of Alloys and Compounds》.2009,第489卷第343–347页. * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102040239A (en) | 2011-05-04 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102040239B (en) | Preparation method of submicron CuS (copper sulphide) classification ball | |
| CN101234779A (en) | Method for preparing copper-indium-sulfur semi-conductor nano particles | |
| CN103771506B (en) | Micro-/to receive hierarchy titanium dioxide microballoon sphere and preparation method thereof and application | |
| CN103213950B (en) | Hydroxides and preparation method of oxide hollow structure nano material of hydroxides | |
| CN110283288B (en) | Heteroatom-doped polymer nano-microsphere with cavity structure capable of being produced in large scale and preparation method thereof | |
| CN103100725A (en) | Preparation method of silver/carbon quantum dot composite nanometer materials | |
| CN103332726B (en) | The hydrothermal synthesis method of tin dioxide nanometer material | |
| CN102633309A (en) | Hydrothermal preparation method for NiS2 with controllable shape | |
| CN102992390B (en) | Method for preparing nano-zinc oxide sol and zinc oxide submicron spheres | |
| CN102910667A (en) | Hydrophilic vermiform CuS (copper sulphide) agglomerate and preparation method and usage thereof | |
| CN104861971B (en) | Tungsten oxide quanta point material and preparation method thereof | |
| CN106693994A (en) | Preparation and application of core-shell structure bismuth sulfide@copper sulfide composite microspheres | |
| CN104944405A (en) | Preparation method of carbon spheres | |
| CN105502340A (en) | Preparation method of fluorescent carbon dots | |
| CN102557107A (en) | Method for preparing flower-shaped copper sulfide (CuS) nanocrystal | |
| CN104692454B (en) | Method for preparing lead sulfide nano-particles through reflux precipitation | |
| Li et al. | In-situ deposition preparation of n-octadecane@ Silica@ Polydopamine-doped polypyrrole microcapsules for photothermal conversion and thermal energy storage of full-spectrum solar radiation | |
| CN111559756A (en) | Light absorption enhanced spherical CuS submicron material and preparation method thereof | |
| CN103058259A (en) | Preparation method for chestnut-shaped copper sulphide hollow micron sphere composed of nanosheets | |
| CN105152208B (en) | Synthetic method of colorful TiO2 microsphere and application of colorful TiO2 microsphere | |
| CN103964401A (en) | Component-controllable copper sulfur selenium nanometer sheet as well as preparation method and application thereof | |
| CN101531393B (en) | Method for preparing zinc sulfide semiconductor nanoparticles | |
| CN102786038B (en) | Hydro-thermal synthesis method of cubic phase InSe nano sheet | |
| CN103145173B (en) | Preparation method of copper sulphide classified nanometer structure material | |
| CN102502774B (en) | Method for preparing bar-shaped copper sulfide (CuS) nanocrystallines by microwave solvothermal method |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20120530 Termination date: 20170118 |