CN101857276A - Method for preparing general nano metal sulphide - Google Patents
Method for preparing general nano metal sulphide Download PDFInfo
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- CN101857276A CN101857276A CN201010207730A CN201010207730A CN101857276A CN 101857276 A CN101857276 A CN 101857276A CN 201010207730 A CN201010207730 A CN 201010207730A CN 201010207730 A CN201010207730 A CN 201010207730A CN 101857276 A CN101857276 A CN 101857276A
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Abstract
The invention discloses a method for preparing general nano metal sulphide. The method is characterized in that: diethyldithio carbamate is adopted as a single-source reaction precursor of the sulphide, and is thermally decomposed, nucleated and grown in the mixed solution of surfactants with different coordination properties to prepare appearance and size-controllable sulphide nanocrystals in a pure state by one step. In the method, the thermal decomposition of the reaction precursor in the high-boiling mixed solution of the surfactants and components of the solution are controlled, and the nucleation and growth process of the nanocrystals is adjusted, so the prepared metal sulphide has the characteristics of pure phase state, uniform size, high yield, relatively higher dispersibility in non-polar organic solvents, easily controlled reaction conditions and large-scale production.
Description
Technical field
The present invention relates to a kind of preparation method of nano metal combination materials, relate in particular to a kind of preparation method of nano metal sulphide, belong to material chemistry technical field.
Background technology
Metallic sulfide has performances such as good light, electricity, magnetic, catalysis, is widely used in semi-conductor, biomedicine, photo-luminescent devices, solar cell, infrared detector, fiber optics communication, pigment, lubricant etc.Along with the application of metallic sulfide is day by day extensive, emerged the preparation method of a collection of nano metal sulphide
For example: plain eastern Gui etc. have been applied for the patent (number of patent application: 02127680.3) of " metallic sulfide and preparation method thereof ".This invention need add a sealed vessel together with metal-powder and sulphur powder, rotate or vibrate described sealed vessel, or rotate rotator in the described sealed vessel, carry out chemical welding and prepare metallic sulfide, and metallic sulfide is pulverized and disperseed.
Jin Xianbo etc. have applied for the patent (number of patent application: 200410060903.5) of " metal sulfurized preparation method ".This invention is that elemental sulfur is placed organic solvent with metal or metal protosulphide, and reaction for a long time obtains metallic sulfide under high temperature, high pressure.
Tang Baizhong has applied for the patent (number of patent application: 200610031191.3) of " a kind of preparation method of nano metal sulphide ".This invention relates to the preparation method of concrete molybdenumdisulphide and tungsten sulfide.With the sour ammonium of hydration molybdenum (tungsten) is molybdenum (tungsten) source, and porous molybdenum oxide (tungsten) is a solid support material, is molybdenum oxide (tungsten) crystal by heating pyrolyze sour ammonium of converted in-situ hydration molybdenum (tungsten) in molybdenum oxide (tungsten) duct; At last, be in 800～1100 ℃ of high-temperature cracking furnaces in temperature, introduce hydrogen sulfide, under the restriction in molybdenum oxide (tungsten) duct, generate moly-sulfide (tungsten) nano material.
Haitao Zhangs etc. have been applied for the patent (number of patent application: 200610088468.6) of " preparation method of nano metal sulphide ".This invention is after transition metal oxide or transition metal powders and thiocarbamide are mixed in proportion, to heat-treat in retort furnace, then its grinding is obtained metallic sulfide.
Bai Hongjuan etc. waits the patent of having applied for preparing with microbial process metallic sulfide respectively with tribute person of outstanding talent in addition, and number of patent application is respectively 200510012417.0 and 200510012619.5.
But comprehensive above-mentioned multiple preparation method exists that preparation condition is harsh relatively, product phase purity is lower, and size and valence state are difficult to problems such as control.
Summary of the invention
In view of the obtained achievement of above-mentioned prior art and the deficiency of existence; purpose of the present invention aims to provide a kind of preparation method of general nano metal sulphide; so that the general preparation method of the higher metallic sulfide of a kind of large-scale production and quality to be provided, further promote the application of metallic sulfide.
Above-mentioned purpose of the present invention, the technical scheme of its realization is:
A kind of preparation method of general nano metal sulphide, it is characterized in that: adopt the single source pre-reaction material of N,N-Diethyldithiocarbamic Acid as sulfide, carry out thermolysis, nucleation and growth in the tensio-active agent mixing solutions of the different coordination characteristics of tool, a step makes the sulfide nano crystal of pure state, pattern and controllable size.
Further, the preparation method of aforementioned a kind of general nano metal sulphide comprises step:
I, the aqueous solution of heavy metallic salt dropwise is added in the aqueous solution that diethyldithiocar bamic acid receives, after filtration, washing and oven dry obtain the pre-reaction material N,N-Diethyldithiocarbamic Acid;
II, the pre-reaction material N,N-Diethyldithiocarbamic Acid is dissolved in the tensio-active agent mixing solutions of the different coordination characteristics of tool, vacuumizes and be warming up to more than 100 ℃, kept 20 minutes～30 minutes;
III, under protection of inert gas, solution is warming up to more than 250 ℃, keep more than 1 hour;
IV, treat that solution naturally cools to room temperature after, add polar solvent, after centrifugal, washing and drying, obtain the nano metal sulphide crystal;
Further, the preparation method of aforementioned a kind of general nano metal sulphide, pre-reaction material described in the step II is the N,N-Diethyldithiocarbamic Acid of single source form.
Further, the preparation method of aforementioned a kind of general nano metal sulphide, wherein the metallic element in this N,N-Diethyldithiocarbamic Acid comprises silver-colored Ag, plumbous Pb, copper Cu, cadmium Cd, bismuth Bi, iron Fe, cobalt Co, nickel, tungsten W, molybdenum Mo, zinc Zn, tin Sn, antimony Sb, titanium Ti, among manganese Mn and the mercury Hg any one; The optional scope of this tensio-active agent comprises chain alkyl acid, alkylamine, long-chain alcohol and ether.
Implement technical scheme of the present invention, compare to its significant advantage of prior art and be:
Select for use N,N-Diethyldithiocarbamic Acid as single source pre-reaction material, by control to pre-reaction material thermal decomposition process and solvent composition in high boiling surfactivity mixed solvent, regulate nanocrystal nucleation and process of growth, the metallic sulfide phase that makes thus is pure, size is even, the productive rate height, and the dispersiveness in non-polar organic solvent is better, easily-controlled reaction conditions, and can scale operation.
For the preparation method who makes a kind of general nano metal sulphide of the present invention is easier to understand the practicality of its substantive distinguishing features and institute's tool thereof, below constipation close accompanying drawing the present invention's one specific embodiment be described in further detail.But following description and explanation about embodiment do not constitute any limitation protection domain of the present invention.
Description of drawings
Fig. 1 is the Fe that makes by the inventive method
3S
4The transmission electron microscope photo of nano particle;
Fig. 2 is Fe shown in Figure 1
3S
4The saturation magnetization graphic representation;
The ZnS quantum dot transmission electron microscope photo that Fig. 3 makes by the inventive method;
Fig. 4 is the photic emitting fluorescence spectrogram of ZnS quantum dot shown in Figure 3.
Embodiment
The preparation method of a kind of general nano metal sulphide provided by the invention utilizes N,N-Diethyldithiocarbamic Acid (DDTC) to heavy metal ion (silver-colored Ag
+, plumbous Pb
2+, copper Cu
2+, cadmium Cd
2+, bismuth Bi
3+, iron Fe
3+, cobalt Co
2+, nickel
2+, tungsten W
2+, molybdenum Mo
2+, zinc Zn
2+, tin Sn
4+, antimony Sb
3+, titanium Ti
3+, manganese Mn
3+With mercury Hg
2+) have complex ability preferably, can form stable title complex, and this title complex is water insoluble.Therefore can be easy to obtain pure Me (DDTC)
xPrecursor.The metallic sulfide that this kind precursor forms after the pyrolytic decomposition nucleation in the tensio-active agent mixing solutions does not dissolve in organic solution, exists with the solid form in reactor, easily realizes the separation and the purification of product.The product of the present invention's preparation is a metallic sulfide powder.
Divided by concrete steps: at first the aqueous solution of heavy metallic salt dropwise is added in the aqueous solution that diethyldithiocar bamic acid receives, forms heavy metal Me (DDTC)
xThe pre-reaction material Me (DDTC) that obtains single source is filtered, washs and dried to precipitation then
xPressed powder; Again with precursor Me (DDTC)
xPressed powder is dissolved in the tensio-active agent mixed solvent of the different coordination characteristics of tool; bleed and be warming up to about 100 ℃; then bleed and leave standstill more than 20 minutes, under protection of inert gas, be warming up to suitable temp (being generally more than 250 ℃) again and keep for some time this precursor Me (DDTC)
xPyrolytic reaction can at high temperature take place; At last, treat that solution naturally cools to room temperature after, add polar solvent (as ethanol etc.), just after centrifugal, washing and drying, can obtain metal sulfide nanocrystal.
In addition, the prioritization scheme of technique scheme can also comprise
1. this pre-reaction material is the N,N-Diethyldithiocarbamic Acid of single source form, and this precursor had both contained metallic element, also contains element sulphur, so can avoid owing to the too high ununiformity that causes the product particle size of partial concn in the reaction process; This kind precursor can form the solution (under the certain temperature) of clear in the tensio-active agent mixing solutions, can guarantee that like this environmental facies of metallic sulfide nucleation in the organic solvent system are same, makes that the sulfide nano crystal that generates is more even.
2. the optional scope of this tensio-active agent comprises chain alkyl acid, alkylamine, long-chain alcohol and ether etc.From concrete enforcement: described mixed solvent is that oleic acid, oleyl amine, stearylamine, octadecylene, cetylamine, the Dodecyl Mercaptan etc. one or more make up allotment in proportion and form, according to the reaction parameter (solvent burden ratio, temperature, time, reactant concn etc.) of precursor in different ligand solvents, control the coordination characteristic of mixed solvent and between crystalline nucleation and growth, keep certain balance.
Below, introduce preparation process of the present invention in detail by two specific embodiments:
Embodiment 1
Ferric diethyldithiocarbamate (Fe (DDTC) with 0.2mmol
3) be raw material; be dissolved in oleic acid, oleyl amine and octadecylene mixed solvent (10mmol: 10mmol: in there-necked flask 20mmol) is housed; bleed and be heated to about 120 ℃; keep 20min; under protection of inert gas, be warming up to 280 ℃ then and kept 1 hour, treat that at last solution naturally cools to room temperature after, add the 50mL dehydrated alcohol; through centrifugal, washing and dry, the black powder of gained is accredited as the Fe of cube phase through X-ray diffraction with transmission electron microscope
3S
4Nano particle (as shown in Figure 1); Nano particle that obtains such as the Fe of Fig. 2
3S
4The saturation magnetization graphic representation shown in have good magnetic.
Embodiment 2
Zinc diethyldithiocarbamate (Zn (DDTC) with 0.2mmol
2) be raw material; be dissolved in oleic acid and oleyl amine mixed solvent (40mmol: in there-necked flask 40mmol) are housed; bleed and be heated to about 100 ℃; keep 30min; under protection of inert gas, be warming up to 300 ℃ then and kept 1 hour, treat that at last solution naturally cools to room temperature after, add the 50mL dehydrated alcohol; centrifugal, washing and dry, the white powder of gained is accredited as the ZnS nano particle (as shown in Figure 3) of six side's phases through X-ray diffraction.The nano particle that obtains has good optical characteristics (as shown in Figure 4).
In sum, the present invention utilizes high boiling point mixed solvent pyrolysated method, by control to precursor thermal decomposition process and solvent composition, realization is to the control of crystal nucleation and process of growth, further can obtain high yield, the size homogeneous is adjustable, pattern is controlled metallic sulfide, and be easy to amplify reaction, be suitable for large-scale industrial production.
Below only be representational two embodiment that have much in the numerous concrete exemplary applications of the present invention, protection scope of the present invention is not constituted any limitation.All employing equivalents or equivalence are replaced and the technical scheme of formation, all drop within the rights protection scope of the present invention.
Claims (5)
1. the preparation method of a general nano metal sulphide, it is characterized in that: adopt the single source pre-reaction material of N,N-Diethyldithiocarbamic Acid as sulfide, carry out thermolysis, nucleation and growth in the tensio-active agent mixing solutions of the different coordination characteristics of tool, a step makes the sulfide nano crystal of pure state, pattern and controllable size.
2. the preparation method of a kind of general nano metal sulphide according to claim 1 is characterized in that comprising step:
I, the aqueous solution of heavy metallic salt dropwise is added in the aqueous solution that diethyldithiocar bamic acid receives, after filtration, washing and oven dry obtain the pre-reaction material N,N-Diethyldithiocarbamic Acid;
II, the pre-reaction material N,N-Diethyldithiocarbamic Acid is dissolved in the tensio-active agent mixing solutions of the different coordination characteristics of tool, vacuumizes and be warming up to more than 100 ℃, kept 20 minutes～30 minutes;
III, under protection of inert gas, solution is warming up to more than 250 ℃, keep more than 1 hour;
IV, treat that solution naturally cools to room temperature after, add polar solvent, after centrifugal, washing and drying, obtain the nano metal sulphide crystal.
3. the preparation method of a kind of general nano metal sulphide according to claim 2, it is characterized in that: pre-reaction material described in the step II is the N,N-Diethyldithiocarbamic Acid of single source form.
4. according to the preparation method of claim 1,2 or 3 described a kind of general nano metal sulphides, it is characterized in that: the metallic element in the described N,N-Diethyldithiocarbamic Acid comprises silver-colored Ag, plumbous Pb, copper Cu, cadmium Cd, bismuth Bi, iron Fe, cobalt Co, nickel, tungsten W, molybdenum Mo, zinc Zn, tin Sn, antimony Sb, titanium Ti, among manganese Mn and the mercury Hg any one.
5. the preparation method of a kind of general nano metal sulphide according to claim 1 and 2, it is characterized in that: the optional scope of described tensio-active agent comprises chain alkyl acid, alkylamine, long-chain alcohol and ether.
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102277157A (en) * | 2011-05-30 | 2011-12-14 | 中国科学院苏州纳米技术与纳米仿生研究所 | Near-infrared silver sulphide quantum dot as well as preparation method and application thereof |
| CN103553130A (en) * | 2013-10-30 | 2014-02-05 | 上海师范大学 | Cu3BiS3 ternary sulfur nano material and preparation method thereof |
| CN103664723A (en) * | 2013-12-18 | 2014-03-26 | 湖南大学 | Preparation methods of dithiocarbamic acid metal salt solution and metal sulfide nano material |
| CN107603619A (en) * | 2017-10-12 | 2018-01-19 | 贵州医科大学 | A kind of sulfide nano luminescent material and preparation method thereof |
| CN108086014A (en) * | 2017-12-30 | 2018-05-29 | 绍兴恒钧环保科技有限公司 | Polyester cotton short route dyeing and finishing technology |
| CN110194931A (en) * | 2019-04-16 | 2019-09-03 | 中国科学院兰州化学物理研究所 | A kind of method of the fabricated in situ vulcanization composite lubricated coating of Nano silver grain reinforced TFE base |
| CN112423912A (en) * | 2018-06-28 | 2021-02-26 | 东邦钛株式会社 | Metal powder, method for producing same, and method for predicting sintering temperature |
| CN112415129A (en) * | 2020-10-26 | 2021-02-26 | 广东韶钢松山股份有限公司 | Method for detecting calcium and magnesium in sintered ore |
| CN115054691A (en) * | 2022-07-15 | 2022-09-16 | 中山大学附属第七医院(深圳) | Ternary sulfur group metal nano particle and preparation method and application thereof |
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Cited By (14)
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|---|---|---|---|---|
| US10421901B2 (en) | 2011-05-30 | 2019-09-24 | Suzhou Institute of Nano-tech and Nano-bionics, Chinese Academy of Sciences | Preparation method of near-infrared silver sulfide quantum dots |
| CN102277157B (en) * | 2011-05-30 | 2014-06-11 | 中国科学院苏州纳米技术与纳米仿生研究所 | Near-infrared silver sulphide quantum dot as well as preparation method and application thereof |
| CN102277157A (en) * | 2011-05-30 | 2011-12-14 | 中国科学院苏州纳米技术与纳米仿生研究所 | Near-infrared silver sulphide quantum dot as well as preparation method and application thereof |
| CN103553130A (en) * | 2013-10-30 | 2014-02-05 | 上海师范大学 | Cu3BiS3 ternary sulfur nano material and preparation method thereof |
| CN103553130B (en) * | 2013-10-30 | 2015-07-15 | 上海师范大学 | Cu3BiS3 ternary sulfur nano material and preparation method thereof |
| CN103664723A (en) * | 2013-12-18 | 2014-03-26 | 湖南大学 | Preparation methods of dithiocarbamic acid metal salt solution and metal sulfide nano material |
| CN107603619B (en) * | 2017-10-12 | 2020-08-04 | 贵州医科大学 | Sulfide nano luminescent material and preparation method thereof |
| CN107603619A (en) * | 2017-10-12 | 2018-01-19 | 贵州医科大学 | A kind of sulfide nano luminescent material and preparation method thereof |
| CN108086014A (en) * | 2017-12-30 | 2018-05-29 | 绍兴恒钧环保科技有限公司 | Polyester cotton short route dyeing and finishing technology |
| CN112423912A (en) * | 2018-06-28 | 2021-02-26 | 东邦钛株式会社 | Metal powder, method for producing same, and method for predicting sintering temperature |
| CN112423912B (en) * | 2018-06-28 | 2023-05-23 | 东邦钛株式会社 | Metal powder, method for producing same, and method for predicting sintering temperature |
| CN110194931A (en) * | 2019-04-16 | 2019-09-03 | 中国科学院兰州化学物理研究所 | A kind of method of the fabricated in situ vulcanization composite lubricated coating of Nano silver grain reinforced TFE base |
| CN112415129A (en) * | 2020-10-26 | 2021-02-26 | 广东韶钢松山股份有限公司 | Method for detecting calcium and magnesium in sintered ore |
| CN115054691A (en) * | 2022-07-15 | 2022-09-16 | 中山大学附属第七医院(深圳) | Ternary sulfur group metal nano particle and preparation method and application thereof |
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Application publication date: 20101013 |