CN102992405B

CN102992405B - Preparation method for molybdenum disulfide nanometer nuclear shell nano-structure

Info

Publication number: CN102992405B
Application number: CN201210524834.3A
Authority: CN
Inventors: 唐华; 唐国钢; 李长生; 杨小飞
Original assignee: Jiangsu University
Current assignee: Jiangsu University
Priority date: 2012-12-10
Filing date: 2012-12-10
Publication date: 2014-08-20
Anticipated expiration: 2032-12-10
Also published as: CN102992405A

Abstract

The invention discloses a preparation method for a molybdenum disulfide nanometer nuclear shell nano-structure. By adopting a solvent thermal synthesis method, the preparation method specially comprises the following steps: (1) dissolving Na2MoO4.2H2O, Na2S and ascorbic acid into a mixed solvent, adding surface active agent, conducting centrifugal agitating to be evenly dispersed into the solution, and finally adjusting the pH value of the solution as 12-14 with acid; (2) agitating the solution obtained from step (1), transferring into a stainless steel reaction kettle, sealing, conducting constant-temperature reaction, cooling to room temperature to obtain reaction product; and (3) separating the reaction product, washing and drying to obtain the molybdenum disulfide nanometer nuclear shell nano-structure. The method is simple in process, and low in cost, the product prepared is high in purity and yield, has an important application in the fields of friction, photochemistry, lithium electricity and the like, and is hopefully used for large-scale industrial production.

Description

A kind of preparation method of molybdenum disulfide nano core-shell nano structure

Technical field

The present invention relates to field of nanometer material technology, particularly, is the preparation method of molybdenum disulfide nano core-shell nano structure .

Background technology

The matrix material of nucleocapsid structure (Core-Shell) is the particle that a class has bilayer or multilayered structure, generally by the core at center and be coated on outside shell and form, owing to changing the material category of core and adjusting shell thickness, can obtain the desirable matrix material with excellent properties, transient metal sulfide nucleocapsid structure and hollow structure have excellent physics and chemistry performance, and have important application in many technical fields such as tribology, drug delivery carrier, photonic crystal, catalyzer and stored energy and high performance composite etc., wherein, MoS ₂the feature with special hexagonal layered structure, by very strong chemical bonds, and combines by weak Van der Waals force in its layer between layers, the strong and interlayer of layer internal key effect relatively a little less than, make the anti-shear ability of interlayer very weak, therefore, MoS ₂there are many peculiar performances and be widely used in the fields such as solid lubrication, hydrogen storage material, storage lithium electrode material, shortening, photochemical catalysis.

The common method of synthesis of nano composite material of core-shell structure has high temperature solid-state method, Rong Jiao – gel method, hydrothermal method etc.; Wherein, the severe reaction conditions of high temperature solid-state method, complex operation, resultant is inhomogeneous, shape is random; The complex steps of Rong Jiao – gel method, cost is high, the easy embrittlement of material, some organic solvents are harmful, and the advantage such as hydrothermal method has that technique is simple, easy to operate, product regular shape, particle diameter are even, and MoS ₂the pertinent literature report of nano core-shell nanostructure is less, and cost is high, complex process, Chinese patent 201210044621.0 is announced the preparation method of the solvent-free nano-fluid of a kind of nucleus-shell-hat structure, adopt direct-reduction process to make the nano molybdenum disulfide particle of surface band hydroxyl, add the coating materials with sulfonic acid group to carry out sulfonation processing, and regulate pH and temperature of reaction, finally, by three replacement amine in the positive and negative charge interaction mortise of strong acid and weak base, remove the nano-fluid that solvent obtains stable homogeneous; But, because nanoparticle is easily reunited in preparation process, the MoS that prior art obtains ₂nano core-shell nanostructure pattern is wayward, and prior art processes is complicated, affects its mass-producing application in the fields such as tribology, photochemistry, catalysis.

Summary of the invention

For the deficiencies in the prior art, one of object of the present invention is to provide the preparation method of molybdenum disulfide nano core-shell nano structure, the object of the present invention is to provide a kind of preparation method of with low cost, technique is simple and productive rate is high molybdenum disulfide nano core-shell nano structure.

(1) obtain solution: by Na ₂moO ₄2H ₂o, Na ₂s, xitix are dissolved in mixed solvent, dissolve and obtain solution, then add tensio-active agent, by centrifugal mixer, it are distributed in solution uniformly, by the pH value of alkali regulator solution, are finally 12 ~ 14; (2) after solution stirring step (1) being obtained, move into stainless steel cauldron, sealing, after isothermal reaction, is cooled to room temperature, obtains reaction product; (3) separated above-mentioned reaction product, washing, vacuum-drying, obtain molybdenum disulfide nano core-shell nano structure.

Described mixed solvent is water-ethylene glycol mixed solvent or water-ethanol mixed solvent, according to volume ratio 1:2, mixes.

Described tensio-active agent is C ₁₃h ₂₂clN cats product.

Na in described solution ₂moO ₄2H ₂the concentration of O is 0.03～0.05 mol/L.

In described solution, Na ₂moO ₄2H ₂o, Na ₂the ratio of the amount of substance of S, xitix is 1.0:2.5 ~ 3.5:1.5 ~ 2.5, preferred 1.0:3.0 ~ 3.5:2.0 ~ 2.5, further preferred 1:3:2.

In described solution, tensio-active agent and Na ₂moO ₄2H ₂the ratio of the amount of substance of O is 1:4 ~ 8, preferred 1:5 ~ 8, further preferred 1:5.

Described temperature of reaction is 160 ℃～200 ℃, and soaking time is 24～48 h.

In preparation process of the present invention, all reagent is commerical prod, does not need to prepare again.

The cost of the inventive method is inexpensive, and production technique is simple and easy to control, and product rate is high, is applicable to large-scale industrial production.

Accompanying drawing explanation

Fig. 1 is the XRD spectra of molybdenum disulfide nano core-shell nano structure;

Fig. 2 is low power field emission scanning electron microscope (SEM) photo of the molybdenum disulfide nano core-shell nano structure that makes of the present invention;

Fig. 3 is high power field emission scanning electron microscope (SEM) photo of the molybdenum disulfide nano core-shell nano structure that makes of the present invention;

Fig. 4 is that the prepared product of embodiment 1 adds the tribological property in whiteruss to.

Embodiment

By embodiment, further describe the present invention below, as known by the technical knowledge, the present invention also can describe by other the scheme that does not depart from the technology of the present invention feature, and therefore changes within the scope of the present invention all or that be equal in the scope of the invention are all included in the invention.

embodiment 1:

By 0.88g Na ₂moO ₄2H ₂o, 0.94g Na ₂s and 0.41g xitix add in alcohol-water (2:1) mixed solvent of 60 ml, dissolve and obtain settled solution, then add 0.30 g C ₂₇h ₅₀clN, after dissolving completely, then uses 2molL ^-1naOH regulate pH value to 12, stir after 30 min, mixed solution is transferred in the stainless steel cauldron of 100 ml, be placed in vacuum drying oven in 180 ℃ of insulation 36 h, be cooled to room temperature, reaction product, after centrifugation, is used respectively deionized water and dehydrated alcohol repetitive scrubbing, last under vacuum condition 80 ℃ of dry 10 h obtain the product powder of grey black, i.e. molybdenum disulfide nano core-shell nano structure.

The XRD figure spectrum explanation XRD peak position of Fig. 1 is consistent with standard diffractogram (PDF No.37-1492), and product is pure MoS ₂nanostructure, Fig. 2 is the low power SEM photo of product, can obviously see a large amount of ball-like structures, wherein some tiny balloon growth not exclusively, form spherical structure in midair, in ball inside in midair, significantly see and have kernel to exist, formed distinct nucleocapsid structure, its diameter is about 500～800 nm, the MoS of thickness 50～100 nm ₂nanometer sheet, the SEM photo that Fig. 3 is high power, further illustrate product diameter be 1～2 um, kernel is 500 about nm, there is obvious flower-like structure in ball outside.

embodiment 2:

By 1.21g Na ₂moO ₄2H ₂o, 1.36g Na ₂s and 1.76g xitix add in ethylene glycol-water (2:1) mixed solvent of 60 ml, dissolve and obtain settled solution, then add 0.27 g C ₂₇h ₅₀clN, after dissolving completely, then uses 2molL ^-1naOH regulate pH value to 14, stir after 30 min, mixed solution is transferred in the stainless steel cauldron of 100 ml, be placed in vacuum drying oven in 160 ℃ of insulation 48h, be cooled to room temperature, reaction product is after centrifugation, use respectively deionized water and dehydrated alcohol repetitive scrubbing, last under vacuum condition 80 ℃ of dry 10 h obtain the product powder of grey black, i.e. molybdenum disulfide nano core-shell nano structure, the XRD figure of embodiment 2 and SEM photo similar embodiment 1.

embodiment 3:

By 0.73g Na ₂moO ₄2H ₂o, 0.59g Na ₂s and 1.06g xitix add in ethylene glycol-water (2:1) mixed solvent of 60 ml, dissolve and obtain settled solution, then add 0.32 g C ₂₇h ₅₀clN, after dissolving completely, then uses 2molL ^-1naOH regulate pH value to 13, stir after 30 min, mixed solution is transferred in the stainless steel cauldron of 100 ml, be placed in vacuum drying oven in 200 ℃ of insulation 24h, be cooled to room temperature, reaction product is after centrifugation, use respectively deionized water and dehydrated alcohol repetitive scrubbing, last under vacuum condition 80 ℃ of dry 10 h obtain the product powder of grey black, i.e. molybdenum disulfide nano core-shell nano structure, the XRD figure of embodiment 3 and SEM photo similar embodiment 1.

embodiment 4:

by the prepared nanometer MoS with nucleocapsid structure of embodiment 1 ₂with general goods MoS ₂add to respectively in paraffin, wherein MoS ₂content be 1%, after ultrasonic being uniformly dispersed, using CETR UMT-2 frictional testing machines to examine and wipe MoS ₂impact on paraffin frictional behaviour, in experiment, disc used is 45# steel, diameter is 2 cm; Ball is 440C stainless steel, and diameter is 10 mm; Rotating speed is 150 r/min, and the time is 30 min.

Fig. 4 is with core-shell nano MoS ₂with commodity MoS ₂influence curve to paraffin frictional behaviour during respectively as additive; As can be seen from Figure, under this experiment condition, nuclear shell structure nano MoS ₂there is less frictional coefficient, and comparatively mild with the variation of its frictional coefficient of increase of load.

Claims

1. a preparation method for molybdenum disulfide nano core-shell nano structure, is characterized in that comprising the steps:

(1) obtain solution: by Na ₂moO ₄2H ₂o, Na ₂s, xitix are dissolved in mixed solvent, dissolve and obtain solution, then add tensio-active agent, by centrifugal mixer, it are distributed in solution uniformly, by the pH value of alkali regulator solution, are finally 12 ~ 14;

(2) after solution stirring step (1) being obtained, move into stainless steel cauldron, sealing, after isothermal reaction, is cooled to room temperature, obtains reaction product;

(3) separated above-mentioned reaction product, washing, vacuum-drying, obtain molybdenum disulfide nano core-shell nano structure;

Described mixed solvent is water-ethylene glycol mixed solvent or water-ethanol mixed solvent, and water mixes according to volume ratio 1:2 with ethylene glycol or ethanol; Described temperature of reaction is 160 ℃～200 ℃, and soaking time is 24～48 h.

2. the preparation method of a kind of molybdenum disulfide nano core-shell nano structure as claimed in claim 1, is characterized in that: described tensio-active agent is C ₁₃h ₂₂clN cats product.

3. the preparation method of a kind of molybdenum disulfide nano core-shell nano structure as claimed in claim 1, is characterized in that: Na in described solution ₂moO ₄2H ₂the concentration of O is 0.03～0.05 mol/L.

4. the preparation method of a kind of molybdenum disulfide nano core-shell nano structure as claimed in claim 1, is characterized in that: in described solution, and Na ₂moO ₄2H ₂o, Na ₂the ratio of the amount of substance of S, xitix is 1.0:2.5 ~ 3.5:1.5 ~ 2.5.

5. the preparation method of a kind of molybdenum disulfide nano core-shell nano structure as claimed in claim 4, is characterized in that: in described solution, and Na ₂moO ₄2H ₂o, Na ₂the ratio of the amount of substance of S, xitix is 1.0:3.0 ~ 3.5:2.0 ~ 2.5.

6. the preparation method of a kind of molybdenum disulfide nano core-shell nano structure as claimed in claim 5, is characterized in that: in described solution, and Na ₂moO ₄2H ₂o, Na ₂the ratio of the amount of substance of S, xitix is 1:3:2.

7. the preparation method of a kind of molybdenum disulfide nano core-shell nano structure as claimed in claim 1, is characterized in that: in described solution, and tensio-active agent and Na ₂moO ₄2H ₂the ratio of the amount of substance of O is 1:4 ~ 8.

8. the preparation method of a kind of molybdenum disulfide nano core-shell nano structure as claimed in claim 7, is characterized in that: in described solution, and tensio-active agent and Na ₂moO ₄2H ₂the ratio of the amount of substance of O is 1:5.