CN101746837A - Preparation method of cobalt sulfide micro tube with hiberarchy structure - Google Patents
Preparation method of cobalt sulfide micro tube with hiberarchy structure Download PDFInfo
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- CN101746837A CN101746837A CN200910218092A CN200910218092A CN101746837A CN 101746837 A CN101746837 A CN 101746837A CN 200910218092 A CN200910218092 A CN 200910218092A CN 200910218092 A CN200910218092 A CN 200910218092A CN 101746837 A CN101746837 A CN 101746837A
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Abstract
The invention belongs to an inorganic chemical synthesis method and in particular relates to a preparation method of a cobalt sulfide micro tube with hiberarchy structure; in the invention, water-soluble cobalt salt is used as a metal source, thioacetamide is used as a sulphur source, ethanediamine is used as metal chelating agent, and cetyl trimethylammonium bromide CTAB is used as a template agent, in a closed reactor, hydro-thermal reaction is carried out under a certain temperature condition, so as to synthesize the micron tube-like cobalt sulfide with the hiberarchy structure, the outer diameter of the tube is about 1.5micron, the thickness of the tube wall is about 400nm, the average length is about 15micron, the tube wall is a nanoscale hexagonal sheet, and the length and the thickness of the sheet are 90nm and 22nm respectively; the synthesis method has the advantages of cheap and easy-obtaining raw material, simple equipment, low reaction temperature and good process repeatability and overcomes the problem of environment pollution caused by organic solvent in the previous synthesis method; the obtained product has wide application prospect in the field of biology, catalysis and material science and the like.
Description
Technical field
The invention belongs to inorganic chemical synthesis method, be specifically related to have the preparation method of hierarchy cobaltous sulfide micron tube.
Background technology
As a kind of important chalcogen compound, cobaltous sulfide has complicated structure and composition and good catalysis, optics, electricity and magnetic performance, have a wide range of applications at industrial circles such as dearomatization and hydrodesulfurization processs, it also is widely used in research fields such as solar cell material in addition.The at present traditional synthetic method and the method for bibliographical information all can't synthesize the cobaltous sulfide micron tube with hierarchy, make the application of cobaltous sulfide be restricted.Such as, " crystal growth and design " (Crystal Growth ﹠amp; Design) 2008 the 8th volumes have reported with the biomolecules to be that the template hydrothermal method is synthesized Co for 3745 pages
3S
4Octahedra nanocrystalline; Britain's " chemical communication " (Chemical Communications) 2003 has reported that vapour deposition process synthesizes the CoS nano wire for 2498 pages, and this method need be in argon shield, carries out under 850 ℃ of hot conditionss; 2621 pages of U.S.'s " inorganic chemistry " (Inorganic Chemistry) 1999 the 38th volumes have reported that the hot method of toluene solvant synthesizes Co
9S
8And CoS
2Nanocrystalline, the raw materials used toxicity of this method is very big, and the cobaltous sulfide pattern that obtains is irregular, reunites easily; 2006 the 16th volumes of Germany " advanced function material " (Advanced Functional Materials) have been reported for 1389 pages and have been utilized Ke Kendaer effect (Kirkendall effect) to synthesize cobaltous sulfide hollow Nano crystalline substance, this synthetic method complicated operation, raw materials used costliness.Other method also has to utilize sacrifices synthetic cobaltous sulfide nanotube (" colloid and interface science " the Journal of Colloid andInterface Science of template, volume was 271 pages in 2007 the 308th), utilize organometallics to prepare film (" chemical vapour deposition " Chemical Vapor Deposition of cobaltous sulfide for presoma, volume was the 91st page in 2005 the 11st), but all can't synthesize micron tube with hierarchy cobaltous sulfide.
Summary of the invention
At existing preparation nanometer cobaltous sulfide technology above shortcomings, the object of the present invention is to provide a kind of preparation method with hierarchy cobaltous sulfide micron tube.Operation is simple and reliable for this method, adopt raw material cheap and easy to get, synthesized the cobaltous sulfide micron tube with hierarchy under lower temperature and pressure condition, the micron tube that obtains has bigger specific surface area and bigger ratio electric capacity, for the widespread use of cobaltous sulfide is laid a good foundation.
Technical scheme provided by the present invention is as follows:
A kind of synthetic method with hierarchy cobaltous sulfide micron tube, it is characterized in that this method with water soluble cobaltous salt, thioacetamide is a raw material, is complexing agent with the quadrol, with cetyl trimethylammonium bromide CTAB is tensio-active agent, preparation cobaltous sulfide micron open tube under hydrothermal condition.Its operation steps is as follows:
(1) under the room temperature, press water: 1: 1 obtain solution of quadrol volume ratio, under the agitation condition 0.0001 mole water soluble cobaltous salt is added in the above-mentioned solution, fully stirred 5 minutes;
(2) the cetyl trimethylammonium bromide CTAB of 0.00010-0.00028 mole is mixed with solution in the step (1), heating makes its dissolving a little;
(3) thioacetamide that will be in excess in 3 times of water soluble cobaltous salt molar weights mixes with the solution of preparation in the step (2), stir after 15 minutes, put into closed reactor, under 160-200 ℃ of temperature condition hydro-thermal reaction 10-24 hour, can synthesize the cobaltous sulfide micron tube, but above-mentioned raw materials proportioning equal proportion is amplified.
Above-mentioned water soluble cobaltous salt can be cobaltous acetate, Xiao Suangu or cobalt chloride.
The present invention compared with prior art, have the following advantages and beneficial effect: reported first of the present invention have the preparation method of hierarchy cobaltous sulfide micron tube, it is poisonous to have overcome the synthetic cobaltous sulfide raw material of existing method, costliness, complex process, problems such as temperature of reaction height; This synthetic method temperature of reaction is lower, and raw material is cheap and easy to get and environment do not polluted, and equipment is simple, good process repeatability; Synthetic product productive rate height, regular shape is for the preparation with hierarchy hollow nano-material provides a practicable thinking of development.Simultaneously, hierarchy cobaltous sulfide micron tube has high-specific surface area, and is bigger than electric capacity, demonstrates good electricity and magnetic performance, for it lays good basis in the applied research in fields such as catalysis, biotechnology, Materials science from now on.
Description of drawings
Accompanying drawing 1 is the x-ray diffractogram of powder of the cobaltous sulfide micron tube that makes under 160 ℃ of the temperature;
Accompanying drawing 2 is the low power electron scanning micrograph of the cobaltous sulfide micron tube that makes under 160 ℃ of the temperature;
Accompanying drawing 4 is the transmission electron microscope photo of the cobaltous sulfide micron tube that makes under 160 ℃ of the temperature.
Embodiment
Embodiment 1:
At first with 4 ml deionized water and 4 milliliters of quadrol thorough mixing, take by weighing 0.0001 mole cobaltous acetate, be added under the agitation condition in the above-mentioned solution, mixing solutions continues to stir 5 minutes; 0.00014 mole cetyl trimethylammonium bromide CTAB is joined in the above-mentioned solution, and heating makes it dissolving a little; Then 0.0003 mole thioacetamide is joined in the above-mentioned mixed solution, stirring in the band teflon-lined stainless steel cauldron of packing into after 15 minutes, sealed reactor was 160 ℃ of reactions 24 hours.Be cooled to room temperature then, open reactor,,, obtain black powder with deionized water and absolute ethanol washing with cloth formula funnel suction filtration.Product is accredited as six side's phase cobaltous sulfide (Co through X-ray powder diffraction
1-xS) (X=0.75) (accompanying drawing 1) identifies that by the low power scanning electronic microscope black powder is a micron tube, and the mean length of pipe is about 15 microns (accompanying drawings 2).High power scanning electronic microscope evaluation tube wall is made up of the hexagon nanometer sheet, and the length of side of sheet and thickness are about 90 nanometers and 22 nanometers (accompanying drawing 3) respectively.Prove further that by transmission electron microscope cobaltous sulfide is empty tubular structure, the external diameter of pipe is approximately 1.5 microns, and thickness of pipe is about 400 nanometers (accompanying drawing 4).The specific surface area of this micron tube is 46.24m
2/ g is 201F/g than electric capacity.The Magnetic Measurement result shows that the cobaltous sulfide micron tube is ferromegnetism at low temperatures.
Embodiment 2:
At first with 4 ml deionized water and 4 milliliters of quadrol thorough mixing, take by weighing 0.0001 mole Xiao Suangu, be added under the agitation condition in the above-mentioned solution, mixing solutions continues to stir 5 minutes; 0.00014 mole cetyl trimethylammonium bromide CTAB is joined in the above-mentioned solution, and heating makes it dissolving a little; Then 0.0003 mole thioacetamide is joined in the above-mentioned mixed solution, stirring in the band teflon-lined stainless steel cauldron of packing into after 15 minutes, sealed reactor was 160 ℃ of reactions 24 hours.Be cooled to room temperature then, open reactor,,, obtain cobaltous sulfide micron tube with embodiment 1 equal length with deionized water and absolute ethanol washing with cloth formula funnel suction filtration.
Embodiment 3:
At first with 4 ml deionized water and 4 milliliters of quadrol thorough mixing, take by weighing 0.0001 mole cobalt chloride, be added under the agitation condition in the above-mentioned solution, mixing solutions continues to stir 5 minutes; 0.00014 mole cetyl trimethylammonium bromide CTAB is joined in the above-mentioned solution, and heating makes it dissolving a little; Then 0.0003 mole thioacetamide is joined in the above-mentioned mixed solution, stirring in the band teflon-lined stainless steel cauldron of packing into after 15 minutes, sealed reactor was 160 ℃ of reactions 24 hours.Be cooled to room temperature then, open reactor,,, obtain cobaltous sulfide micron tube with embodiment 1 equal length with deionized water and absolute ethanol washing with cloth formula funnel suction filtration.
Embodiment 4:
At first with 4 ml deionized water and 4 milliliters of quadrol thorough mixing, take by weighing 0.0001 mole cobaltous acetate, be added under the agitation condition in the above-mentioned solution, mixing solutions continues to stir 5 minutes; 0.00010 mole cetyl trimethylammonium bromide CTAB is joined in the above-mentioned solution, and heating makes it dissolving a little; Then 0.0003 mole thioacetamide is joined in the above-mentioned mixed solution, stirring in the band teflon-lined stainless steel cauldron of packing into after 15 minutes, sealed reactor was 160 ℃ of reactions 24 hours.Be cooled to room temperature then, open reactor, with cloth formula funnel suction filtration, with deionized water and absolute ethanol washing, obtain the cobaltous sulfide micron tube, the mean length of pipe is about 10 microns.
Embodiment 5:
At first with 4 ml deionized water and 4 milliliters of quadrol thorough mixing, take by weighing 0.0001 mole cobaltous acetate, be added under the agitation condition in the above-mentioned solution, mixing solutions continues to stir 5 minutes; 0.00028 mole cetyl trimethylammonium bromide CTAB is joined in the above-mentioned solution, and heating makes it dissolving a little; Then 0.0004 mole thioacetamide is joined in the above-mentioned mixed solution, stirring in the band teflon-lined stainless steel cauldron of packing into after 15 minutes, sealed reactor was 160 ℃ of reactions 24 hours.Be cooled to room temperature then, open reactor, with cloth formula funnel suction filtration, with deionized water and absolute ethanol washing, obtain the cobaltous sulfide micron tube, the mean length of pipe is about 12 microns.
Embodiment 6:
At first with 4 ml deionized water and 4 milliliters of quadrol thorough mixing, take by weighing 0.0001 mole cobaltous acetate, be added under the agitation condition in the above-mentioned solution, mixing solutions continues to stir 5 minutes; 0.00014 mole cetyl trimethylammonium bromide CTAB is joined in the above-mentioned solution, and heating makes it dissolving a little; Then 0.0003 mole thioacetamide is joined in the above-mentioned mixed solution, stirring in the band teflon-lined stainless steel cauldron of packing into after 15 minutes, sealed reactor was 180 ℃ of reactions 15 hours.Be cooled to room temperature then, open reactor, with cloth formula funnel suction filtration, with deionized water and absolute ethanol washing, obtain the cobaltous sulfide micron tube, the mean length of pipe is about 14 microns.
Embodiment 7:
At first with 4 ml deionized water and 4 milliliters of quadrol thorough mixing, take by weighing 0.0001 mole cobaltous acetate, be added under the agitation condition in the above-mentioned solution, mixing solutions continues to stir 5 minutes; 0.00014 mole cetyl trimethylammonium bromide CTAB is joined in the above-mentioned solution, and heating makes it dissolving a little; Then 0.0003 mole thioacetamide is joined in the above-mentioned mixed solution, stirring in the band teflon-lined stainless steel cauldron of packing into after 15 minutes, sealed reactor was 200 ℃ of reactions 10 hours.Be cooled to room temperature then, open reactor, with cloth formula funnel suction filtration, with deionized water and absolute ethanol washing, obtain the cobaltous sulfide micron tube, the mean length of pipe is about 14 microns.
Claims (3)
1. the cobaltous sulfide micron tube with hierarchy is characterized in that it is to have Co
1-xThe micron tube that forms by the hexagon nanometer sheet that S forms, wherein X is 0.75; The mean length of described micron tube is 15 microns, and external diameter is about 1.5 microns, and thickness of pipe is about 400 nanometers.
2. according to claim 1 described preparation method, it is characterized in that this method comprises the steps: with hierarchy cobaltous sulfide micron tube
(1) under the room temperature, press water: 1: 1 obtain solution of quadrol volume ratio, under the agitation condition 0.0001 mole water soluble cobaltous salt is added in the above-mentioned solution, fully stirred 5 minutes;
(2) 0.00014 mole cetyl trimethylammonium bromide CTAB is mixed with solution in the step (1), heating makes its dissolving;
(3) thioacetamide that will be in excess in 3 times of water soluble cobaltous salt molar weights mixes with the solution of preparation in the step (2), stirs after 15 minutes, puts into closed reactor, under 160-200 ℃ of temperature condition hydro-thermal reaction 10-24 hour, can synthesize the cobaltous sulfide micron tube.
3. according to claim 2 described methods, it is characterized in that: described water soluble cobaltous salt is cobaltous acetate, Xiao Suangu or cobalt chloride.
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Cited By (11)
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| CN102502887A (en) * | 2011-11-23 | 2012-06-20 | 陕西科技大学 | Method for preparing cobalt sulfide nanocrystals by hydrothermal-assisted sonochemistry |
| CN102502888A (en) * | 2011-11-23 | 2012-06-20 | 陕西科技大学 | Microwave-hydrothermal preparation method for cobalt sulfide nanometer crystals |
| CN103545116A (en) * | 2013-09-24 | 2014-01-29 | 安徽师范大学 | Foamed nickel-nanometer eight-vulcanization and nine-cobalt composite material, preparation method for same and super-capacitor electrode |
| CN104399494A (en) * | 2014-12-10 | 2015-03-11 | 吉林大学 | Carbon-coated cobalt sulfide material as well as preparing method thereof and application of carbon-coated cobalt sulfide material in aspect of water cracking hydrogen production |
| CN104016419B (en) * | 2014-06-14 | 2015-10-21 | 哈尔滨工业大学 | The three-dimensional flower-shaped CoS hierarchy of dye sensitization solar battery is to the preparation method of electrode |
| CN106799242A (en) * | 2015-11-26 | 2017-06-06 | 中国科学院大连化学物理研究所 | A kind of surface amphiphilic nano vulcanization Co catalysts and preparation method and application |
| CN109250746A (en) * | 2017-07-13 | 2019-01-22 | 首都师范大学 | A kind of porous water-soluble sulfide photothermal conversion nano material can be applied to tumor thermal therapy and its hydrothermal synthesis method |
| CN109873156A (en) * | 2019-02-18 | 2019-06-11 | 上海交通大学 | A kind of preparation method and its battery assembly of high capacity Mg secondary cell cobalt sulfide positive electrode |
| CN110627133A (en) * | 2019-10-24 | 2019-12-31 | 山东大学 | Cobalt sulfide Co1-xPreparation method of S hexagonal plate aggregate material |
| CN111081983A (en) * | 2019-12-26 | 2020-04-28 | 陕西科技大学 | Co9S8Preparation method of self-supporting cathode of carbon felt sodium ion battery |
| CN112850800A (en) * | 2021-01-29 | 2021-05-28 | 中南大学 | Method for preparing two-dimensional CoS nanosheet based on chemical vapor deposition method |
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| CN107244699B (en) * | 2017-05-18 | 2019-08-20 | 武汉纺织大学 | A kind of preparation method and applications of the cobalt sulfide of the three-dimensional cyclic micro-nano structure with nanoscale twins assembling |
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| CN102502887A (en) * | 2011-11-23 | 2012-06-20 | 陕西科技大学 | Method for preparing cobalt sulfide nanocrystals by hydrothermal-assisted sonochemistry |
| CN102502888A (en) * | 2011-11-23 | 2012-06-20 | 陕西科技大学 | Microwave-hydrothermal preparation method for cobalt sulfide nanometer crystals |
| CN102502887B (en) * | 2011-11-23 | 2014-03-12 | 陕西科技大学 | Method for preparing cobalt sulfide nanocrystals by hydrothermal-assisted sonochemistry |
| CN102502888B (en) * | 2011-11-23 | 2014-07-02 | 陕西科技大学 | Microwave-hydrothermal preparation method for cobalt sulfide nanometer crystals |
| CN103545116A (en) * | 2013-09-24 | 2014-01-29 | 安徽师范大学 | Foamed nickel-nanometer eight-vulcanization and nine-cobalt composite material, preparation method for same and super-capacitor electrode |
| CN104016419B (en) * | 2014-06-14 | 2015-10-21 | 哈尔滨工业大学 | The three-dimensional flower-shaped CoS hierarchy of dye sensitization solar battery is to the preparation method of electrode |
| CN104399494A (en) * | 2014-12-10 | 2015-03-11 | 吉林大学 | Carbon-coated cobalt sulfide material as well as preparing method thereof and application of carbon-coated cobalt sulfide material in aspect of water cracking hydrogen production |
| CN104399494B (en) * | 2014-12-10 | 2016-04-20 | 吉林大学 | The coated cobalt sulfide material of a kind of carbon, preparation method and the application in water-splitting product hydrogen thereof |
| CN106799242A (en) * | 2015-11-26 | 2017-06-06 | 中国科学院大连化学物理研究所 | A kind of surface amphiphilic nano vulcanization Co catalysts and preparation method and application |
| CN106799242B (en) * | 2015-11-26 | 2019-08-09 | 中国科学院大连化学物理研究所 | A kind of surface amphiphilic nano vulcanization Co catalysts and the preparation method and application thereof |
| CN109250746A (en) * | 2017-07-13 | 2019-01-22 | 首都师范大学 | A kind of porous water-soluble sulfide photothermal conversion nano material can be applied to tumor thermal therapy and its hydrothermal synthesis method |
| CN109250746B (en) * | 2017-07-13 | 2020-12-01 | 首都师范大学 | Porous water-soluble sulfide photothermal conversion nano material applicable to tumor photothermal treatment and hydrothermal synthesis method thereof |
| CN109873156A (en) * | 2019-02-18 | 2019-06-11 | 上海交通大学 | A kind of preparation method and its battery assembly of high capacity Mg secondary cell cobalt sulfide positive electrode |
| CN110627133A (en) * | 2019-10-24 | 2019-12-31 | 山东大学 | Cobalt sulfide Co1-xPreparation method of S hexagonal plate aggregate material |
| CN111081983A (en) * | 2019-12-26 | 2020-04-28 | 陕西科技大学 | Co9S8Preparation method of self-supporting cathode of carbon felt sodium ion battery |
| CN112850800A (en) * | 2021-01-29 | 2021-05-28 | 中南大学 | Method for preparing two-dimensional CoS nanosheet based on chemical vapor deposition method |
| CN112850800B (en) * | 2021-01-29 | 2022-03-25 | 中南大学 | Method for preparing two-dimensional CoS nanosheet based on chemical vapor deposition method |
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