CN104386753B - A kind of preparation method of molybdenum disulfide nano tube - Google Patents

A kind of preparation method of molybdenum disulfide nano tube Download PDF

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CN104386753B
CN104386753B CN201410676448.5A CN201410676448A CN104386753B CN 104386753 B CN104386753 B CN 104386753B CN 201410676448 A CN201410676448 A CN 201410676448A CN 104386753 B CN104386753 B CN 104386753B
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molybdenum disulfide
nano tube
disulfide nano
molybdenum
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CN104386753A (en
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凤仪
刘文宏
钱刚
苗世顶
豆亚坤
黄晓晨
丁冬冬
汤海
张学斌
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Hefei University of Technology
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G39/00—Compounds of molybdenum
    • C01G39/06—Sulfides
    • 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
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/01—Particle morphology depicted by an image
    • C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/10—Particle morphology extending in one dimension, e.g. needle-like
    • C01P2004/13—Nanotubes

Abstract

The preparation method who the invention discloses a kind of molybdenum disulfide nano tube, is characterized in that: taking fibrous carbon nano material as template, make the coated C-MoS of molybdenum bisuphide of homogeneous2Coaxial Nanotubes; Then at mobile CO2The coated C-MoS of the molybdenum bisuphide of homogeneous described in high-temperature calcination under atmosphere2Coaxial Nanotubes, to remove carbon component, obtains molybdenum disulfide nano tube. The wall thickness of the molybdenum disulfide nano tube that the present invention obtains can be by changing C-MoS2MoS in Coaxial Nanotubes2Coating thickness is controlled, and the present invention is in the place of fibrous carbon nano-material surface projection or sharp bend, coated breach or the fracture of there will be of molybdenum bisuphide, the molybdenum disulfide nano tube of preparation also there will be corresponding fault of construction thus, these defects can increase the edge active sites of nanotube surface, make it have more excellent photoelectricity and catalytic performance.

Description

A kind of preparation method of molybdenum disulfide nano tube
One, technical field
The present invention relates to a kind of preparation method of molybdenum disulfide nano tube.
Two, background technology
Molybdenum bisuphide is the lamellar compound of class Graphene, and its construction unit is made up of three layers of atom, i.e. each Mo (IV) atomIn the center of triangular prism, and with six sulphur atom coordinations, sulphur atom layer is distributed in two of Mo atomic layer with covalent bondsLimit, forms the layer structure that is similar to sandwich. Unique layer structure makes its nanostructured that can form many novelties, asThe faint Van der Waals force of interlayer makes it be easy to be stripped from into even individual layer nanometer sheet of monodispersed multilayer, the inside of these nanometer sheetWith the atom bond valence at edge be different, inner atom is saturated, and the atom at edge is undersaturated, forms dangling bonds,Be edge active sites, in addition, thin layer molybdenum bisuphide is also very soft, is easy to bending, is therefore easy to be subject to the impact of external environment,Its edge active sites is cross-linked with each other and forms nano particle or the nanotube stablizing and there is fullerene structure.
In various structures, MoS2Nanotube progressively receives scholar's concern because of its potential application, and alumina formwork method canPreparation MoS2The array of nanotube, (DongboYu, etal., MaterialsResearchBulletin46 (2011) 1504-1509)But earning rate is too little, be difficult to apply on a large scale. Conversion method (SifeiZhuo, etal., the Angewandte of presoma nano wireChemieInternationalEdition125 (2013) 8764-8768) and C60Catalysis method (MajaRemskaretal., Science292 (2001) 479-481) also can prepare molybdenum disulfide nano tube, but these methods are also not suitable for preparing bending nanotube,And the wall thickness of nanotube is also difficult to control. Therefore, need to develop a kind of method of simple environmental protection controlled to prepare on a large scale structureMolybdenum disulfide nano tube.
Three, summary of the invention
The present invention is for avoiding the existing weak point of above-mentioned prior art, and a kind of preparation method of molybdenum disulfide nano tube is provided,The technical barrier overcoming is at mobile CO2Under atmosphere, C-MoS is removed in high-temperature calcination2Carbon component in Coaxial Nanotubes,Obtain molybdenum disulfide nano tube
Technical solution problem of the present invention, adopts following technical scheme:
The preparation method of molybdenum disulfide nano tube of the present invention, its feature is: taking fibrous carbon nano material as template, make allThe coated C-MoS of molybdenum bisuphide of matter2Coaxial Nanotubes; Then at mobile CO2Two sulphur of homogeneous described in high-temperature calcination under atmosphereChange the coated C-MoS of molybdenum2Coaxial Nanotubes, to remove carbon component, obtains molybdenum disulfide nano tube;
Described CO2Purity be 80-100%, flow velocity is 1-10000mL/min;
The calcining heat of described high-temperature calcination is 600 DEG C～1500 DEG C, and calcination time is 1h～96h.
The preparation method of molybdenum disulfide nano tube of the present invention, its feature is also: described fibrous carbon nano material is carbon nanometerPipe, carbon nano-fiber, carbon nanocoils, carbon containing polymer nano-wire or carbon containing macromolecule nano-tube.
The wall thickness of described molybdenum disulfide nano tube can be by changing C-MoS2MoS in Coaxial Nanotubes2Coating thickness is controlled.
The coated C-MoS of the molybdenum bisuphide of homogeneous in raw material of the present invention2Co-axial nano tube preparation method is:
Molybdate (ammonium molybdate or sodium molybdate) is dissolved in distilled water, adds sulfide (vulcanized sodium or ammonium sulfide) and qualityThe ammoniacal liquor of concentration 28-30% reacts 2 hours at 50-90 DEG C, after reaction finishes, in 2-10 DEG C of standing crystallization 48 hours, filtersAnd air drying, obtain four thio ammonium molybdate crystal. Polyethylene glycol (PEG400) and four thio ammonium molybdate are dissolved in distilled waterIn, then add fibrous carbon nano material, ultrasonic dispersion 1h, through centrifugal, washing and 60 DEG C dry after, 850 DEG C of hydrogen gasUnder atmosphere, calcine the coated C-MoS of molybdenum bisuphide that obtains homogeneous after 2h2Coaxial Nanotubes.
The concrete preparation process of the present invention is as follows:
1, the preparation of four thio ammonium molybdate: molybdate is dissolved in the water, adds the ammoniacal liquor of sulfide and mass concentration 28-30%At 50-90 DEG C, react 2 hours, after reaction finishes, in 2-10 DEG C of standing crystallization 48 hours, filter, air drying, obtains four sulphurFor ammonium molybdate crystal; (preparation method is shown in patent application 200410039454.6)
2, the coated C-MoS of the molybdenum bisuphide of homogeneous2The preparation of Coaxial Nanotubes: polyethylene glycol (PEG400) and tetrathio molybdenumAcid ammonium is dissolved in distilled water, then adds fibrous carbon nano material, and ultrasonic dispersion 1h, after centrifugal, washing and 60 DEG CAfter dry, under 850 DEG C of hydrogen atmospheres, calcine the coated C-MoS of molybdenum bisuphide that obtains homogeneous after 2h2Coaxial Nanotubes. (systemPreparation Method is shown in: LiuWenhongetal., ElectrochimicaActa144 (2014) 119 – 126)
3、MoS2The preparation of nanotube: by the C-MoS coated molybdenum bisuphide of homogeneous2Coaxial Nanotubes is put into tube furnace, twoIn carbonoxide atmosphere, this compound of high-temperature calcination, to remove carbon template, obtains MoS2Nanotube. MoS2The pipe thickness of nanotubeCan be by changing MoS2Coating thickness is controlled.
Compared with prior art, the invention has the advantages that:
1, the present invention is by the coated C-MoS of high-temperature calcination molybdenum bisuphide under carbon dioxide atmosphere2Coaxial Nanotubes, therebyObtain molybdenum disulfide nano tube, the method environmental protection, can avoid the generation of waste water, has also avoided loaded down with trivial details last handling process;
2, the present invention finds under study for action, and in fibrous carbon nano-material surface projection or bending place, molybdenum bisuphide is coatedThere will be defect, the molybdenum disulfide nano tube forming thus also has many faults of construction, and these defects make it form more multiple edgeActive sites, has potential photoelectricity and catalytic performance;
3, the wall thickness of the prepared molybdenum disulfide nano tube of the present invention can be by changing MoS2The thickness of clad is controlled, systemPreparation Method is flexible and changeable.
Four, brief description of the drawings
Fig. 1 is the TEM figure of the embodiment of the present invention 1 gained molybdenum disulfide nano tube;
Fig. 2 is the HRTEM figure of the dissimilar indentation, there of the embodiment of the present invention 1 gained molybdenum disulfide nano tube, and wherein (a) isBreach, (b) is incomplete breach completely;
Fig. 3 is the XRD figure of the embodiment of the present invention 1 gained molybdenum disulfide nano tube;
Fig. 4 is the HRTEM figure of the molybdenum disulfide nano tube of the embodiment of the present invention 2 and embodiment 3 gained different wall, wherein(a) be the nanotube of the about 5nm of embodiment 2 gained pipe thickness; (b) be the nanometer of the about 18nm of embodiment 3 gained pipe thicknessPipe.
Five, detailed description of the invention
Embodiment 1:
The present embodiment is prepared molybdenum disulfide nano tube as follows:
5g ammonium molybdate is dissolved in distilled water, adds the ammoniacal liquor of 40mL ammonium sulfide solution and 20mL mass concentration 28-29%,At 60-70 DEG C, react 2 hours, after reaction finishes, in 2-10 DEG C of standing crystallization 48 hours, filter and air drying, obtain tetrathioAmmonium molybdate crystal;
3g four thio ammonium molybdate crystal and 2mL polyethylene glycol are dissolved in successively in 50mL distilled water and obtain mixed liquor, then add0.5g CNT, ultrasonic dispersion is centrifugal after 1 hour, successively with distilled water and absolute ethanol washing and in 60 DEG C dry, then existUnder hydrogen shield, in 850 DEG C of calcinings 2 hours, be cooled to the coated C-MoS of molybdenum bisuphide that obtains homogeneous after room temperature2Co-axial nanoPipe.
By the C-MoS coated molybdenum bisuphide of 2g homogeneous2Coaxial Nanotubes is put into tube furnace, is 60mL/min two at flow velocityIn carbonoxide atmosphere, 850 DEG C of calcining 20h, obtain MoS2Nanotube.
The MoS that the present embodiment is prepared2The TEM of nanotube and HRTEM figure respectively as depicted in figs. 1 and 2, can from figureGo out, nanotube is bending, and has two kinds of different breach. Prepared MoS2The XRD of nanotube as shown in Figure 3, canSee, this nanotube is 2H type molybdenum bisuphide.
Embodiment 2:
The present embodiment is prepared molybdenum disulfide nano tube as follows:
5g ammonium molybdate is dissolved in distilled water, adds the ammoniacal liquor of 40mL ammonium sulfide solution and 20mL mass concentration 28-29%,At 60-70 DEG C, react 2 hours, after reaction finishes, in 2-10 DEG C of standing crystallization 48 hours, filter and air drying, obtain tetrathioAmmonium molybdate crystal;
0.5g four thio ammonium molybdate crystal and 2mL polyethylene glycol are dissolved in successively in 50mL water and obtain mixed liquor, then add0.5g carbon nano-fiber, ultrasonic dispersion is centrifugal after 1 hour, successively with distilled water and absolute ethanol washing and in 60 DEG C dry, thenUnder hydrogen shield, in 850 DEG C of calcinings 2 hours, be cooled to the coated C-MoS of molybdenum bisuphide that obtains homogeneous after room temperature2Co-axial nanoPipe.
By the C-MoS coated molybdenum bisuphide of 4g homogeneous2Coaxial Nanotubes is put into tube furnace, is 100mL/min two at flow velocityIn carbonoxide atmosphere, 900 DEG C of calcining 85h, obtain MoS2Nanotube, its HRTEM, can from figure as shown in Fig. 4 (a)Go out, the wall thickness of prepared molybdenum disulfide nano tube is 5nm.
Embodiment 3:
The present embodiment is prepared molybdenum disulfide nano tube as follows:
5g ammonium molybdate is dissolved in distilled water, adds the ammoniacal liquor of 40mL ammonium sulfide solution and 20mL mass concentration 28-29%,At 60-70 DEG C, react 2 hours, after reaction finishes, in 2-10 DEG C of standing crystallization 48 hours, filter and air drying, obtain tetrathioAmmonium molybdate crystal;
3g four thio ammonium molybdate crystal and 2mL polyethylene glycol are dissolved in successively in 50mL water and obtain mixed liquor, then add 0.5gCarbon nanocoils, ultrasonic dispersion is centrifugal after 1 hour, successively with distilled water and absolute ethanol washing and in 60 DEG C dry, then at hydrogenUnder protection, in 850 DEG C of calcinings 2 hours, be cooled to the coated C-MoS of molybdenum bisuphide that obtains homogeneous after room temperature2Coaxial Nanotubes.
By the C-MoS coated molybdenum bisuphide of 4g homogeneous2Coaxial Nanotubes is put into tube furnace, is 100mL/min two at flow velocityIn carbonoxide atmosphere, 750 DEG C of calcining 86h, obtain MoS2Nanotube, its HRTEM, can from figure as shown in Fig. 4 (b)Find out, the wall thickness of prepared molybdenum disulfide nano tube is 18nm.
Comparative example 2 and embodiment 3 are known, and the wall thickness of gained molybdenum disulfide nano tube of the present invention can be by changing C-MoS2WithMoS in axle nanotube2Coating thickness is controlled.
Embodiment 4:
The present embodiment is prepared molybdenum disulfide nano tube as follows:
5g ammonium molybdate is dissolved in distilled water, adds the ammoniacal liquor of 40mL ammonium sulfide solution and 20mL mass concentration 28-29%,At 60-70 DEG C, react 2 hours, after reaction finishes, in 2-10 DEG C of standing crystallization 48 hours, filter and air drying, obtain tetrathioAmmonium molybdate crystal;
3g four thio ammonium molybdate crystal and 2mL polyethylene glycol are dissolved in successively in 50mL water and obtain mixed liquor, then add 0.5gCNT, ultrasonic dispersion is centrifugal after 1 hour, successively with distilled water and absolute ethanol washing and in 60 DEG C dry, then at hydrogenUnder protection, in 850 DEG C of calcinings 2 hours, be cooled to the coated C-MoS of molybdenum bisuphide that obtains homogeneous after room temperature2Coaxial Nanotubes.
By the C-MoS coated molybdenum bisuphide of 8g homogeneous2Coaxial Nanotubes is put into tube furnace, is 10000mL/min at flow velocityCarbon dioxide atmosphere in, 700 DEG C calcining 46h, obtain MoS2Nanotube.

Claims (3)

1. a preparation method for molybdenum disulfide nano tube, is characterized in that: taking fibrous carbon nano material as template, make allThe coated C-MoS of molybdenum bisuphide of matter2Coaxial Nanotubes; Then at mobile CO2Under atmosphere described in high-temperature calcination two of homogeneousThe C-MoS that molybdenum sulfide is coated2Coaxial Nanotubes, to remove carbon component, obtains molybdenum disulfide nano tube;
Described CO2Purity be 80-100%, flow velocity is 1-10000mL/min;
The calcining heat of described high-temperature calcination is 600 DEG C～1500 DEG C, and calcination time is 1h～96h.
2. preparation method according to claim 1, is characterized in that: described fibrous carbon nano material be CNT,Carbon nano-fiber, carbon nanocoils, carbon containing polymer nano-wire or carbon containing macromolecule nano-tube.
3. preparation method according to claim 1, is characterized in that: the wall thickness of described molybdenum disulfide nano tube is by changingC-MoS2MoS in Coaxial Nanotubes2Coating thickness is controlled.
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CN104900867B (en) * 2015-05-25 2017-04-12 哈尔滨工业大学 Preparation method of CNT/Co/MoS2 composite material
CN105645471B (en) * 2016-04-08 2017-10-03 合肥工业大学 A kind of method that nanometer fibrous poly- molybdic acid class material cures prepare molybdenum disulfide nano tube
CN106145190A (en) * 2016-06-15 2016-11-23 南开大学 The preparation method of a kind of molybdenum disulfide nano tube and the application in lithium ion battery thereof
CN106206034A (en) * 2016-07-01 2016-12-07 南京清辉新能源有限公司 A kind of multifunctional electrodes for Line of light electric flux device and preparation method thereof
CN106964362A (en) * 2017-04-10 2017-07-21 中国科学技术大学 Metal molybdate/carbon composite nano-fiber and preparation method thereof and composite and its application
CN108103766B (en) * 2017-12-29 2021-07-30 澄江市力点科技有限公司 Molybdenum disulfide composite fiber photocatalyst for sewage treatment and preparation method thereof
CN108745380A (en) * 2018-06-28 2018-11-06 合肥工业大学 A kind of preparation method carrying silver-colored molybdenum disulfide nano tube composite electro catalytic liberation of hydrogen material
CN109256546A (en) * 2018-09-03 2019-01-22 山西煤炭进出口集团科学技术研究院有限公司 A kind of molybdenum disulfide/graphene composite material and its preparation method and application

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CN101704552A (en) * 2009-10-28 2010-05-12 无锡润鹏复合新材料有限公司 Molybdenum disulfide nano tube and preparation method thereof

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