CN108557889A - The preparation method of molybdenum disulfide-halloysite nanotubes composite material - Google Patents
The preparation method of molybdenum disulfide-halloysite nanotubes composite material Download PDFInfo
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- CN108557889A CN108557889A CN201810358797.0A CN201810358797A CN108557889A CN 108557889 A CN108557889 A CN 108557889A CN 201810358797 A CN201810358797 A CN 201810358797A CN 108557889 A CN108557889 A CN 108557889A
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- C01G39/00—Compounds of molybdenum
- C01G39/06—Sulfides
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Abstract
The preparation method of molybdenum disulfide halloysite nanotubes composite material of the present invention, is related to composite material, prepares molybdenum disulfide halloysite nanotubes composite material using microwave-hydrothermal method, step is：Prepare halloysite nanotubes；Prepare the reactant feed mixed liquor of molybdate, sulfide and halloysite nanotubes；By the reactant feed mixed liquor pour into ptfe autoclave be placed in microwave hydrothermal equipment complete reactant microwave-hydrothermal method it is effectively compound；Molybdenum disulfide halloysite nanotubes composite material is made in the washed drying of microwave-hydrothermal method products therefrom.The prior art prepared the present invention overcomes molybdenum disulfide composite material molybdenum disulfide composite material in drying or annealing process is easy to reassemble or stack and preparation process is complicated, reaction time is long, high energy consumption and defect of high cost.
Description
Technical field
Technical scheme of the present invention is related to composite material, specifically molybdenum disulfide-halloysite nanotubes composite material
Preparation method.
Background technology
Molybdenum disulfide is a kind of typical stratiform transient metal sulfide, every two layers of sulphur atom layer sandwich, one layer of molybdenum original
Sublayer forms typical sandwich structure, is covalent bond between molybdenum atom and sulphur atom, between adjacent two molecular layer by comparing
Weak Van der Waals force is connected, and effect is compared with strong, interlaminar action is relatively weak in layer.Due to this special layer structure so that
Molybdenum disulfide has good catalysis, lubrication and the performances such as photoelectricity, be widely used in lithium ion cell electrode and photocatalysis,
Solid lubrication, sensor, field-effect transistor technical field.
Molybdenum disulfide is since the unsaturation of its structural edge has higher reactivity, in addition, molybdenum disulfide is narrow
Gap semiconductor has preferable assimilation effect to visible light, in terms of having been applied in photocatalysis.Following documents reports curing
Application of the molybdenum in photocatalysis field：Document MoS2-GO nanocomposites synthesized via a
hydrothermal hydrogel method for solar light photocatalytic degradation of
methylene blue(Y Ding,Y Zhou,W Nie,et al.MoS2-GO nanocomposites synthesized
via a hydrothermal hydrogel method for solar light photocatalytic degradation
Of methylene blue [J] .Applied Surface Science, 2015,357: 1606-1612.) it describes using one
One-step hydrothermal prepares MoS2- GO hydrogel composite materials；CN107233900A discloses a kind of molybdenum disulfide composite Nano golden light
Catalyst and preparation method thereof；CN106902847A disclose a kind of molybdenum disulfide/barium titanate ultrasound visible light catalyst and its
Preparation and application.In photocatalysis field application, the molybdenum disulfide nano sheet of prior art preparation is easily reunited, and makes exposure
Active site is reduced, and influences giving full play to for photocatalysis performance, the above-mentioned existing skill for preparing molybdenum disulfide composite photocatalyst material
Art is long there is also the period, manufacturing cost is higher, preparation process is complicated and the higher many defects of energy consumption.
Cathode of the molybdenum disulfide as lithium ion battery, is easy to the insertion of lithium ion since interlamellar spacing is larger, can make to fill
Discharge capacity is effectively increased, but leads to lithium ion battery since particle crushes during the lithiumation-repeated takes off lithium
The cyclical stability of charge and discharge is poor.To solve the above-mentioned problems, the negative material for being used as lithium ion battery in the prior art is main
Using the composite material of two kinds of molybdenum disulfide, i.e. molybdenum disulfide-graphene composite material and molybdenum disulfide-carbon composite.Text
Offer Facile synthesis and electrochemical properties of two dimensional layered
MoS2/graphene composite for reversible lithium storage(X Zhou,Z Wang,W Chen,
et al.Facile synthesis and electrochemical properties of two dimensional
layered MoS2/graphene composite for reversible lithium storage[J].Journal of
Power Sources, 2014,251 (2): 264-268.) it describes molybdenum disulfide/graphene composite wood is prepared using hydro-thermal method
Material；CN107394184A discloses a kind of molybdenum disulfide/graphene nano belt composite with loose three-dimensional winding arrangement
And its preparation method and application；CN104319102A discloses that a kind of to prepare the three-dimensional flower-shaped graphene/molybdenum disulfide of load compound
Method of the threadiness of material to electrode；Above-mentioned molybdenum disulfide-graphene composite material defect of the existing technology for preparing is：
Such composite material is easy to reassemble or stack in drying or annealing process, this greatly reduces specific surface area, limits
The transport of electronics and ion also needs to high annealing in some preparation methods, and manufacturing cycle is longer, cost is higher.
CN107256949A discloses the preparation method of platelike molybdenumdisulfide/carbon composite；CN104966817A discloses curing
The three-dimensional porous network composite material and preparation method of molybdenum and carbon；CN107275600A disclose the molybdenum disulfide of hollow sphere/
The preparation method of carbon composite；CN106423218A discloses a kind of synthetic method of molybdenum disulfide/carbon nano-composite material；
CN104934602A discloses a kind of molybdenum disulfide/carbon composite and preparation method thereof；CN106410136A discloses one kind
Layer structure molybdenum disulfide/carbon composite and the preparation method and application thereof；It is above-mentioned that prepare molybdenum disulfide-carbon composite existing
Technology has a defect that：It carries out compound being the carbon material synthesized by carbon source with molybdenum disulfide, wherein use sol-gel
The entire experimental period of method is longer；Need to introduce template using hydro-thermal method, and template also needs to handle or remove again；Using change
That learns vapour deposition process needs progress high temperature vapor deposition, and combined coefficient is relatively low and easy tos produce by-product, influences product quality.
The method of prior art preparation molybdenum disulfide composite material mainly has chemical vapour deposition technique, high temperature solid-state method, is total to
The precipitation method, sol-gel method and hydro-thermal method.Chemical vapour deposition technique requires experiment condition high, controllability and poor repeatability.It is high
Warm solid phase method prepares that larger product granularity, high energy consumption, efficiency are low, are easy to be mixed into impurity.Coprecipitation reacts complicated in the liquid phase,
Control difficulty is big, may will produce reunion when precipitating reagent is added or composition is not uniform enough.Raw material used in sol-gel method is normal
It is related to organic matter and expensive, it is longer the time required to entire sol-gel process.Existing hydro-thermal method is long there are reaction time,
The defect of high energy consumption.
Invention content
The technical problem to be solved by the present invention is to：The preparation side of molybdenum disulfide-halloysite nanotubes composite material is provided
Method is to prepare molybdenum disulfide-galapectite using microwave-hydrothermal method using molybdate, sulfide and halloysite nanotubes as raw material
Nanometer tube composite materials, overcome molybdenum disulfide composite material preparation the prior art in drying or annealing process molybdenum disulfide
Composite material is easy to reassemble or stack and preparation process is complicated, reaction time is long, high energy consumption and defect of high cost.
Technical solution is used by the present invention solves the technical problem：Molybdenum disulfide-halloysite nanotubes composite material
Preparation method, be as follows：
The first step prepares halloysite nanotubes：
It is 1: 3~5 to weigh the HCl solution of the desired amount of galapectite and 0.3~5mol/L in container by solid-liquid mass ratio
Then mixing, 3~6h of hydro-thermal under the conditions of temperature is 60~80 DEG C filter and are washed with deionized 5~7 extremely neutrality, will
Filter cake is placed in 60~80 DEG C of baking ovens and is dried to drying, then grinds and cross 200 mesh sieve, the galapectite powder purified, by 0.3
The NaOH solution of~6mol/L is added in the galapectite powder of purification obtained above, and it is 1: 10~50 to make solid-liquid mass ratio,
Temperature carries out 1~2h of supersound process under the conditions of being 50~70 DEG C, then filters and washs 5~7 times, until pH value is neutrality, it will
Gained filter cake is placed in 60~80 DEG C of baking ovens dry 10~12h, takes out grinding and crosses 200 mesh sieve, obtains halloysite nanotubes,
It is spare；
Second step prepares reactant feed mixed liquor：
The molybdate, 10~150mmol sulfide and the above-mentioned first step systems of 0.3~3.0g of 1~20mmol are weighed respectively
The molybdate weighed, is first dissolved in 35~175mL deionized waters by the halloysite nanotubes obtained, to be mixed complete to molybdate
Dissolving, then the sulfide weighed is dissolved in above-mentioned molybdate solution, 20~50min of magnetic agitation, to be mixed at room temperature
Liquid halloysite nanotubes made from the above-mentioned first step weighed is added, magnetic force stirs at room temperature in after homogeneous transparent state
30~60min is mixed, then 10~30min of ultrasound, preparation obtains reactant feed mixed liquor；
Third walks, and the microwave-hydrothermal method of reactant is effectively compound：
The reactant feed mixed liquor that above-mentioned second step is prepared is poured into the polytetrafluoroethylene (PTFE) that volume is 50~250mL
In reaction kettle, compactedness is 50%~70%, which is placed in microwave hydrothermal equipment, and setting temperature is
170~230 DEG C, pressure is that 2~4MPa is cooled to room temperature, the microwave-hydrothermal method for completing reactant is effectively multiple after keeping the temperature 1~5h
It closes；
4th step prepares molybdenum disulfide-halloysite nanotubes composite material：
Above-mentioned third is walked to the microwave-hydrothermal method effectively compound obtained product for completing reactant from polytetrafluoroethyl-ne alkene reaction
It is taken out in kettle, 4~6 washings is carried out with deionized water, dry 12 under the conditions of temperature is 60~80 DEG C~for 24 hours, obtain two
Molybdenum sulfide-halloysite nanotubes composite material.
The preparation method of above-mentioned molybdenum disulfide-halloysite nanotubes composite material, the molybdate are ammonium molybdate, magnesium molybdate
Or alkali metal molybdate.
The preparation method of above-mentioned molybdenum disulfide-halloysite nanotubes composite material, the sulfide are thioacetamide, sulphur
Urea or L-cysteine.
The preparation method of above-mentioned molybdenum disulfide-halloysite nanotubes composite material, the microwave hydrothermal equipment are multipurpose
Microwave chemosynthesis instrument, microwave hydrothermal reaction or microwave hydrothermal parallel projects instrument.
The preparation method of above-mentioned molybdenum disulfide-halloysite nanotubes composite material, the compactedness are that filler accounts for poly- four
The percent by volume of vinyl fluoride reaction kettle.
The preparation method of above-mentioned molybdenum disulfide-halloysite nanotubes composite material, the raw material are commercially available, institute
What the equipment being related to was known in the art, involved process operation is that those skilled in the art will appreciate that.
The beneficial effects of the invention are as follows：Compared with prior art, substantive distinguishing features outstanding possessed by the present invention are as follows：
(1) galapectite is a kind of natural porous nano tubulose silicate mineral, alumina octahedral sheet and silicon in structure
Space between oxygen tetrahedral layer does not match that dislocation promotes flat crystal to be curled into pipe, when synusia twists, oxygen-octahedron layer
Outside, including alumina octahedral sheet, the dioctahedron type structure of 1: 1 type structural unit layer is formed.Due to this unique structure,
So that galapectite have larger specific surface area, can be used for adsorbing, be catalyzed and electrochemistry in terms of application.
Molybdenum disulfide is carried on halloysite nanotubes by the present invention, the two can under certain condition shown excellent
Synergistic effect.Reason is：Molybdenum disulfide nano sheet is easily reunited, and so that exposed active site is reduced, is influenced photocatalysis
Etc. performances give full play to.And large specific surface area, the good dispersion of halloysite nanotubes, halloysite nanotubes are introduced as function
Carrier regulation and control molybdenum disulfide nano sheet structure can effectively reduce curing while improving molybdenum disulfide nano sheet pattern
The reunion of molybdenum nanometer sheet increases the active site quantity of material.Therefore, molybdenum disulfide-halloysite nanotubes that the present invention is built
Composite material not only has important theory significance, is also with a wide range of applications.
(2) the method for the present invention utilizes the property of halloysite nanotubes, the serious flower-shaped molybdenum disulfide that can will reunite micro-
It is evenly dispersed nanometer sheet that spherical structure, which improves, and the nanometer sheet is regularly grown on halloysite nanotubes, to
A kind of novel molybdenum disulfide-halloysite nanotubes composite material is arrived.
(3) compared with prior art, the present invention has following substantive distinguishing characteristics：
1) CN107233900A discloses a kind of molybdenum disulfide composite nano-gold photochemical catalyst and preparation method thereof, this is compound
Material is to first pass through chemical synthesis to prepare spherical molybdenum disulfide nano particle, then be prepared using sol-gel method.It prepares
Complex process, complex steps, the period is longer, and also needs to calcine in nitrogen atmosphere high temperature, and energy consumption is higher.The present invention utilizes day
Right mineral are effectively compound by microwave-hydrothermal method progress with molybdenum disulfide, are effectively improved while with the shorter reaction time
The pattern of molybdenum disulfide；Compared with gold chloride, galapectite also has many advantages, such as cheap, resourceful as natural minerals.
2) CN106902847A discloses a kind of molybdenum disulfide/barium titanate ultrasound visible light catalyst and its prepares and answer
With the preparation of the molybdenum disulfide/barium titanate composite material uses hydro-thermal method, manufacturing cycle longer.The present invention utilizes natural minerals
It is effectively compound by microwave-hydrothermal method progress with molybdenum disulfide, two sulphur are effectively improved while with more short reaction time
Change the pattern of molybdenum, and compare barium titanate, the galapectite that the present invention uses also has the advantages that cheap and resourceful.
3) it is multiple to disclose a kind of molybdenum disulfide/graphene nanobelt with loose three-dimensional winding arrangement by CN107394184A
Condensation material and its preparation method and application, the preparation of the composite material is other than using hydro-thermal method, it is also necessary to high annealing, energy consumption
It is higher.The present invention be carried out by microwave-hydrothermal method using natural minerals and molybdenum disulfide it is effectively compound, with shorter anti-
The pattern of molybdenum disulfide is effectively improved while between seasonable；Compared with graphene, galapectite also has price as natural minerals
The advantages that cheap, resourceful.
4) CN104319102A discloses a kind of fiber for preparing and loading three-dimensional flower-shaped graphene/molybdenum disulfide composite material
Shape is to the method for electrode, and using hydro-thermal method, manufacturing cycle is longer for the preparation of the molybdenum disulfide/graphene composite material.The present invention
It is effectively compound by microwave-hydrothermal method progress with molybdenum disulfide using natural minerals, it is effective while with more short reaction time
Ground improves the pattern of molybdenum disulfide；Compared to graphene oxide, the galapectite that the present invention uses also has cheap and money
The abundant advantage in source.
5) CN107256949A discloses the preparation method of platelike molybdenumdisulfide/carbon composite, in the preparation method with
Molybdenum disulfide carries out compound being the carbon material synthesized by carbon source, needs high-temperature calcination in an inert atmosphere, energy consumption higher.This
Outside, longer entire experimental period using sol-gel method.The present invention passes through microwave-hydrothermal method using natural minerals and molybdenum disulfide
Progress is effectively compound, and the pattern of molybdenum disulfide is effectively improved while with the shorter reaction time；Compared with carbon material, angstrom
Lip river masonry also has many advantages, such as cheap, resourceful for natural minerals.
6) CN104966817A discloses the three-dimensional porous network composite material and preparation method of molybdenum disulfide and carbon, the system
It carries out with molybdenum disulfide compound being carbon material in Preparation Method, needs to calcine in argon gas atmosphere high temperature, energy consumption is higher.In addition,
Using chemical vapour deposition technique, require height, combined coefficient relatively low experiment condition.The present invention utilizes natural minerals and molybdenum disulfide
It is effectively compound by microwave-hydrothermal method progress, the pattern of molybdenum disulfide is effectively improved while with the shorter reaction time；
Compared with carbon material, galapectite also has many advantages, such as cheap, resourceful as natural minerals.
7) CN107275600A discloses the preparation method of molybdenum disulfide/carbon composite of hollow sphere, the preparation side
It carries out with molybdenum disulfide compound being carbon material in method, complex process needs to introduce template, and templated silicas is wasted
Fall, uses hydro-thermal method longer experimental period in addition.The present invention is carried out with molybdenum disulfide by microwave-hydrothermal method using natural minerals
It is effectively compound, the pattern of molybdenum disulfide is effectively improved while with the shorter reaction time；Compared with carbon material, galapectite
Also have many advantages, such as natural minerals cheap, resourceful.
8) CN106423218A discloses a kind of synthetic method of molybdenum disulfide/carbon nano-composite material, the preparation method
In carry out compound being carbon material with molybdenum disulfide, need high-temperature calcination under an inert atmosphere, energy consumption is higher, is by metal in addition
It after molybdenum ion is complexed with humic acid essence potassium, then calcines with sodium sulphate mixed grinding, may mix uneven, cause product uneven
It is even, it is second-rate.The present invention is effectively compound by microwave-hydrothermal method progress with molybdenum disulfide using natural minerals, with more
The pattern of molybdenum disulfide is effectively improved while the short reaction time；Compared with carbon material, galapectite also has as natural minerals
Have the advantages that cheap, resourceful.
9) CN104934602A discloses a kind of molybdenum disulfide/carbon composite and preparation method thereof, in the preparation method
It carries out compound being carbon material with molybdenum disulfide, complex process, complex steps, cost are higher, and need by high-temperature calcination, energy
Consumption is higher.The present invention is effectively compound by microwave-hydrothermal method progress with molybdenum disulfide using natural minerals, with shorter
The pattern of molybdenum disulfide is effectively improved while reaction time；Compared with carbon material, galapectite also has valence as natural minerals
The advantages that lattice are cheap, resourceful.
10) CN106410136A discloses a kind of layer structure molybdenum disulfide/carbon composite and preparation method thereof and answers
With carrying out with molybdenum disulfide compound being carbon material in the preparation method, complex process needs to carry out high temperature vapor deposition, energy
Consumption is higher, and has hydrogen sulfide gas and generate and enter environment, and there is corrosivity also to easy to produce by-product.The present invention is to utilize day
Right mineral are effectively compound by microwave-hydrothermal method progress with molybdenum disulfide, are effectively improved while with the shorter reaction time
The pattern of molybdenum disulfide；Compared with carbon material, galapectite also has many advantages, such as cheap, resourceful as natural minerals.
(4) in the prior art, there is not yet related prepare molybdenum disulfide-halloysite nanotubes composite wood using microwave-hydrothermal method
The document report of material.
Compared with prior art, the present invention has marked improvement as follows：
(1) the method for the present invention is using molybdate, sulfide and halloysite nanotubes as raw material, using microwave hydrothermal legal system
Standby molybdenum disulfide-halloysite nanotubes composite material overcomes gained molybdenum disulfide in the prior art and its composite material dry
It is easy to reassemble or stack in dry or annealing process and preparation process is complicated, the period is long, high energy consumption and of high cost lacks
It falls into.
(2) galapectite has many advantages, such as cheap, resourceful as natural minerals, adds to natural resources natural minerals
To utilize, its application range is widened and has saved cost.
(3) the method for the present invention can be effectively improved the pattern of molybdenum disulfide, and product pattern is good and uniform, and prepares work
Skill has good repeatability.
(4) the method for the present invention uses microwave-hydrothermal method, reaction to be done directly in the liquid phase, and reaction dissolvent only has deionization
Water, preparation process green, environmental protection, economical while easy to operate, reaction time is short.
Description of the drawings
Fig. 1 is the transmission electron microscope picture of molybdenum disulfide-halloysite nanotubes composite material prepared by the method for the present invention.
Specific implementation mode
Fig. 1 is the transmission electron microscope picture of molybdenum disulfide-halloysite nanotubes composite material prepared by the method for the present invention.It is existing
It is the shapes such as flower-like microsphere that molybdenum disulfide nano sheet prepared by technical method, which is easy to reunite, dispersed poor.The figure shows this hair
Bright introducing halloysite nanotubes as function carrier, make molybdenum disulfide dimensional homogeneity and dispersibility be improved significantly, and
The nanometer sheet is regularly grown on halloysite nanotubes, to obtain a kind of novel molybdenum disulfide-galapectite nanometer
Pipe composite material.
Embodiment 1
The first step prepares halloysite nanotubes：
It is that 1: 3 HCl solution for weighing the desired amount of galapectite and 0.3mol/L mixes in container by solid-liquid mass ratio,
Temperature is hydro-thermal 3h under the conditions of 60 DEG C, then filters and is washed with deionized 5 times to neutrality, filter cake is placed in 60 DEG C of baking ovens
It is dried to drying, then grinds and cross 200 mesh sieve, the NaOH solution of 0.3mol/L is added the galapectite powder purified
In the galapectite powder for the purification stated, it is 1: 10 to make solid-liquid mass ratio, is ultrasonically treated under the conditions of temperature is 50 DEG C
Then 1h is filtered and is washed 5 times, until pH value is neutrality, gained filter cake is placed in 60 DEG C of baking ovens dry 10h, takes out grinding
It is sieved with 200 mesh are crossed, obtains halloysite nanotubes, it is spare；
Second step prepares reactant feed mixed liquor：
Galapectite made from the ammonium molybdate, 10mmol thioacetamides and the above-mentioned first steps of 0.3g of 1mmol is weighed respectively
The ammonium molybdate weighed is first dissolved in 35mL deionized waters by nanotube, to be mixed to be completely dissolved to ammonium molybdate, then will be weighed
Thioacetamide be dissolved in above-mentioned ammonium molybdate solution, magnetic agitation 20min at room temperature, liquid to be mixed is in homogeneous transparent state
Afterwards, halloysite nanotubes made from the above-mentioned first step weighed are added, at room temperature magnetic agitation 30min, it is then ultrasonic
10min, preparation obtain reactant feed mixed liquor；
Third walks, and the microwave-hydrothermal method of reactant is effectively compound：
The reactant feed mixed liquor that above-mentioned second step is prepared is poured into the polytetrafluoroethyl-ne alkene reaction that volume is 50mL
In kettle, which is placed in multipurpose microwave chemosynthesis instrument by compactedness 50%, and setting temperature is
It 170 DEG C, pressure 2MPa, after keeping the temperature 1h, is cooled to room temperature, the microwave-hydrothermal method for completing reactant is effectively compound；
4th step prepares molybdenum disulfide-halloysite nanotubes composite material：
Above-mentioned third is walked to the microwave-hydrothermal method effectively compound obtained product for completing reactant, 4 are carried out with deionized water
Secondary washing, dry 12h, obtains molybdenum disulfide-halloysite nanotubes composite material under the conditions of temperature is 60 DEG C.
Embodiment 2
The first step prepares halloysite nanotubes：
It is that 1: 4 HCl solution for weighing the desired amount of galapectite and 2.6mol/L mixes in container by solid-liquid mass ratio,
Temperature is hydro-thermal 4h under the conditions of 70 DEG C, then filters and is washed with deionized 6 times to neutrality, filter cake is placed in 70 DEG C of baking ovens
It is dried to drying, then grinds and cross 200 mesh sieve, the galapectite powder purified the NaOH solution of 3mol/L is added above-mentioned
In the galapectite powder of obtained purification, it is 1: 30 to make solid-liquid mass ratio, is ultrasonically treated under the conditions of temperature is 60 DEG C
Then 1.5h is filtered and is washed 6 times, until pH value is neutrality, gained filter cake is placed in 70 DEG C of baking ovens dry 11h, taking-up is ground
200 mesh sieve is ground and crossed, halloysite nanotubes are obtained, it is spare；
Second step prepares reactant feed mixed liquor：
Galapectite nanometer made from the magnesium molybdate, 80mmol thiocarbamides and the above-mentioned first steps of 1.5g of 10mmol is weighed respectively
The magnesium molybdate weighed, is first dissolved in 100mL deionized waters by pipe, to be mixed to be completely dissolved to magnesium molybdate, then will be weighed
Thiocarbamide is dissolved in above-mentioned molybdic acid magnesium solution, at room temperature magnetic agitation 35min, liquid to be mixed be in homogeneous transparent state after, by institute
Halloysite nanotubes made from the above-mentioned first step weighed are added, at room temperature magnetic agitation 45min, and then ultrasound 20min, matches
Reactant feed mixed liquor is made；
Third walks, and the microwave-hydrothermal method of reactant is effectively compound：
The reactant feed mixed liquor that above-mentioned second step is prepared is poured into the polytetrafluoroethyl-ne alkene reaction that volume is 150mL
In kettle, which is placed in microwave hydrothermal reaction by compactedness 60%, and setting temperature is 200 DEG C, pressure
Power is 3MPa, after keeping the temperature 3h, is cooled to room temperature, the microwave-hydrothermal method for completing reactant is effectively compound；
4th step prepares molybdenum disulfide-halloysite nanotubes composite material：
Above-mentioned third is walked to the microwave-hydrothermal method effectively compound obtained product for completing reactant, 5 are carried out with deionized water
Secondary washing, dry 18h, obtains molybdenum disulfide-halloysite nanotubes composite material under the conditions of temperature is 70 DEG C.
Embodiment 3
The first step prepares halloysite nanotubes：
It is that 1: 5 HCl solution for weighing the desired amount of galapectite and 5mol/L mixes in container by solid-liquid mass ratio, in temperature
Degree is hydro-thermal 6h under the conditions of 80 DEG C, then filters and is washed with deionized 7 times to neutrality, filter cake is placed in 80 DEG C of baking ovens and is dried
To drying, 200 mesh sieve is then ground and crosses, above-mentioned obtain is added in the NaOH solution of 6mol/L by the galapectite powder purified
To purification galapectite powder in, make solid-liquid mass ratio be 1: 50, temperature be 70 DEG C under the conditions of carry out supersound process 2h, so
It filters and washs 7 times afterwards, until pH value is neutrality, gained filter cake is placed in 80 DEG C of baking ovens dry 12h, takes out grinding and mistake
200 mesh sieve, and obtain halloysite nanotubes, spare；
Second step prepares reactant feed mixed liquor：
The alkali metal molybdate, 150mmolL- cysteines and the above-mentioned first steps of 3.0g for weighing 20mmol respectively are made
Halloysite nanotubes, first the alkali metal molybdate weighed is dissolved in 175mL deionized waters, it is to be mixed to alkali metal molybdic acid
Salt is completely dissolved, then the L-cysteine weighed is dissolved in above-mentioned alkali metal molybdate solution, at room temperature magnetic agitation
Halloysite nanotubes made from the above-mentioned first step weighed are added in after homogeneous transparent state for 50min, liquid to be mixed,
Magnetic agitation 60min at room temperature, then ultrasound 30min, preparation obtain reactant feed mixed liquor；
Third walks, and the microwave-hydrothermal method of reactant is effectively compound：
The reactant feed mixed liquor that above-mentioned second step is prepared is poured into the polytetrafluoroethyl-ne alkene reaction that volume is 250mL
In kettle, which is placed in microwave hydrothermal parallel projects instrument by compactedness 70%, and setting temperature is 230
DEG C, pressure 4MPa is cooled to room temperature, the microwave-hydrothermal method for completing reactant is effectively compound after keeping the temperature 5h；
4th step prepares molybdenum disulfide-halloysite nanotubes composite material：
Above-mentioned third is walked to the microwave-hydrothermal method effectively compound obtained product for completing reactant, 6 are carried out with deionized water
Secondary washing is dried for 24 hours under the conditions of temperature is 80 DEG C, obtains molybdenum disulfide-halloysite nanotubes composite material.
In above-described embodiment, the compactedness is the percent by volume that filler accounts for ptfe autoclave；The original
Material is commercially available, what involved equipment was known in the art, and involved process operation is art technology
What personnel will appreciate that.
Claims (4)
1. the preparation method of molybdenum disulfide-halloysite nanotubes composite material, it is characterised in that be as follows：
The first step prepares halloysite nanotubes：
It is that 1: 3~5 HCl solutions for weighing the desired amount of galapectite and 0.3~5mol/L mix in container by solid-liquid mass ratio,
Then 3~6h of hydro-thermal under the conditions of temperature is 60~80 DEG C filters and is washed with deionized 5~7 times to neutrality, filter cake is set
It is dried to drying in 60~80 DEG C of baking ovens, then grinds and cross 200 mesh sieve, the galapectite powder purified, by 0.3~
The NaOH solution of 6mol/L is added in the galapectite powder of purification obtained above, and it is 1: 10~50 to make solid-liquid mass ratio, in temperature
Degree carries out 1~2h of supersound process under the conditions of being 50~70 DEG C, then filters and washs 5~7 times, until pH value is neutrality, by institute
It obtains filter cake and is placed in 60~80 DEG C of baking ovens dry 10~12h, take out grinding and cross 200 mesh and sieve, obtain halloysite nanotubes, it is standby
With；
Second step prepares reactant feed mixed liquor：
It weighs respectively made from the molybdate, 10~150mmol sulfide and the above-mentioned first steps of 0.3~3.0g of 1~20mmol
The molybdate weighed is first dissolved in 35~175mL deionized waters by halloysite nanotubes, to be mixed completely molten to molybdate
It solves, then the sulfide weighed is dissolved in above-mentioned molybdate solution, at room temperature 20~50min of magnetic agitation, liquid to be mixed
After homogeneous transparent state, halloysite nanotubes made from the above-mentioned first step weighed are added, at room temperature magnetic agitation
30~60min, then 10~30min of ultrasound, preparation obtain reactant feed mixed liquor；
Third walks, and the microwave-hydrothermal method of reactant is effectively compound：
The reactant feed mixed liquor that above-mentioned second step is prepared is poured into the polytetrafluoroethyl-ne alkene reaction that volume is 50~250mL
In kettle, compactedness be 50%~70%, which is placed in microwave hydrothermal equipment, setting temperature be 170~
230 DEG C, pressure is that 2~4MPa is cooled to room temperature, the microwave-hydrothermal method for completing reactant is effectively compound after keeping the temperature 1~5h；
4th step prepares molybdenum disulfide-halloysite nanotubes composite material：
Above-mentioned third is walked to the microwave-hydrothermal method effectively compound obtained product for completing reactant from ptfe autoclave
It takes out, 4~6 washings is carried out with deionized water, dry 12 under the conditions of temperature is 60~80 DEG C~for 24 hours, obtain curing
Molybdenum-halloysite nanotubes composite material.
2. the preparation method of molybdenum disulfide-halloysite nanotubes composite material according to claim 1, it is characterised in that：Institute
It is ammonium molybdate, magnesium molybdate or alkali metal molybdate to state molybdate.
3. the preparation method of molybdenum disulfide-halloysite nanotubes composite material according to claim 1, it is characterised in that：Institute
It is thioacetamide, thiocarbamide or L-cysteine to state sulfide.
4. the preparation method of molybdenum disulfide-halloysite nanotubes composite material according to claim 1, it is characterised in that：Institute
It is multipurpose microwave chemosynthesis instrument, microwave hydrothermal reaction or microwave hydrothermal parallel projects instrument to state microwave hydrothermal equipment.
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| CN111250032A (en) * | 2020-02-26 | 2020-06-09 | 上海电力大学 | Preparation method and application of magnetic fly ash/molybdenum disulfide composite material |
| CN111477855A (en) * | 2020-04-24 | 2020-07-31 | 喻明兵 | Mesoporous carbon coated MoS2The negative electrode material of the sodium ion battery and the preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111250032A (en) * | 2020-02-26 | 2020-06-09 | 上海电力大学 | Preparation method and application of magnetic fly ash/molybdenum disulfide composite material |
| CN111477855A (en) * | 2020-04-24 | 2020-07-31 | 喻明兵 | Mesoporous carbon coated MoS2The negative electrode material of the sodium ion battery and the preparation method thereof |
| CN115382548A (en) * | 2022-08-05 | 2022-11-25 | 浙江工业大学 | Halloysite-based CoAl-LDH microsphere composite material and application thereof |
| CN115382548B (en) * | 2022-08-05 | 2023-09-05 | 浙江工业大学 | Halloysite-based CoAl-LDH microsphere composite material and application thereof |
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